Note: Descriptions are shown in the official language in which they were submitted.
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Detergent Compositions
Technical Field
The present invention relates to bleach-containing detergents. This technology
may find
an application in laundry detergent compositions, soaking detergent
compositions, or any
other compositions for household applications or the like.
Background of the Invention
When detergent products are stored in a geographical location that has a hot
and/or humid
climate, an industrial environment, a household environment, or any
combination thereof,
where a high temperature and a high relative humidity are prevalent, it has
been found
that the mean particle size of the detergent composition increases during
storage of the
product. This increase in mean particle size, gives the product a coarse
appearance of an
aged product, which is not acceptable to the consumers, especially when the
product is of
a hand-wash application.
For many years, the laundry industry have been trying to determine the cause
of this
mean particle size increase of the detergent composition, with little success.
However, the
inventors have now successfully identified the cause of this mean particle
size increase of
the detergent composition during storage.
The laundry industry have been using perborate as a source of available oxygen
in
granular bleach-containing detergent compositions for use in hot or humid
environments.
The inclusion of a bleaching system in a granular detergent formulation helps
to improve
the cleaning performance of the detergent and is common practice in the
laundry
industry.
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The inventors have found that in granular bleach-containing detergent
compositions, it is
the perborate that causes the increase in the mean particle size of the
detergent
composition during storage in conditions of high temperature and high relative
humidity.
Whilst not intending to be bound by theory, it is thought that in these
conditions, sodium
perborate monohydrate is hydrated to sodium perborate tetrahydrate. Sodium
perborate
tetrahydrate forms a gel that binds other detergent ingredients, thus forming
detergent
components of an irregular and increased size. This increase in the mean
particle size of
the detergent components results in a product that is of coarse appearance and
not
acceptable to the consumers.
The inventors have suprisingly found that when selected sodium percarbonate is
used
instead of sodium perborate as a source of available oxygen in a granular
bleach-
containing detergent composition with a bulk density of less than 570g/1, the
problem of
increasing particle sizes is alleviated. It has been found that when such
products are
stored under hot and/or humid conditions, for example, after being
simultaneously
exposed to 32°C and 80% relative humidity for 24 hours, the detergent
composition
retains its main particle size, in that it has a mean particle size of 100% to
130% of the
original mean particle size. This results in a product that remains attractive
to the
consumer, which is of great benefit to the laundry industry and is especially
applicable to
handwash applications.
Also, the inventors have found that, after storage in such, the detergent
composition
retains its bulk density, in that it has a bulk density of 90% to 100% of the
original bulk
density. This results in a product that can still be effectively and
accurately dosed during
the washing process.
By using specifically selected sodium percarbonate in detergent compositions,
namely
sodium percarbonate which comprises less than 2% by weight chloride ions or
sodium
percarbonate prepared by a fluidised bed process, the inventors have found
that detergent
compositions comprising said sodium percarbonate are particularly stable.
Summary of the Invention
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Summary of the Invention
The invention provides a granular bleach-containing detergent composition with
a bulk
density of less than 570g/1, characterised in that the detergent composition
comprises a
percarbonate source, and that, after being openly exposed simultaneously to
32°C and
80% relative humidity for 24 hours, the detergent composition has a mean
particle size of
100% to 130% of the original mean particle size.
The invention also provides a granular bleach-containing detergent composition
with a
bulk density of less than 570g/1 comprising a percarbonate source and less
than 0.06% by
weight extractable suds suppressing silicone, where the percarbonate source
comprises a
salt of percarbonate, characterised in that percarbonate source comprises less
than 2% by
weight chloride ions.
The invention is applicable to detergent compositions that are stored in a
climate
comprising conditions of high temperature and high relative moisture content.
Detailed Description of the Invention
Detergent Composition
The granular bleach-containing detergent composition has a bulk density of
less than
570g/1, preferably from 200g/1 to SSOg/I, more preferably from 300g/1 to
SSOg/l, even
more preferably from 400g/1 to SOOg/l.
The granular bleach-containing detergent composition comprises a percarbonate
source
that comprises a salt of percarbonate, preferably sodium percarbonate,
although in
addition other forms of percarbonate can also be comprised by the percarbonate
source of
the invention. Also, in addition to percarbonate, other sources of available
oxygen known
in the art, or a combination thereof, can be included in the granular
detergent
composition, although it is preferred that percarbonate is the only perhydrate
component
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included in the granular detergent composition.
Mean particle size
The mean particle size of the detergent composition is the mean particle size
of all of the
particles that the detergent composition comprises.
The granular detergent composition comprises a percarbonate source and
optionally
additional detergent ingredients. When the granular detergent composition is
exposed to
conditions of 32°C and 80% relative humidity for 24 hours, after
exposure to these
conditions, the detergent composition has a mean particle size of 100% to
130%,
preferably 100% to 120%, more preferably 100% to 110% of the original mean
particle
size.
For the purpose of this invention, this is determined by the following:
1 OOg of detergent composition comprising 20% by weight alkyl sulphate
surfactant in a
blown powder, less than 2% by weight other cationic or anionic, surfactants in
a blown
powder, 25% by weight sodium tripolyphosphate surfactants in a blown powder,
6% by
weight 1.6 ratio silicate surfactants in a blown powder, 15% by weight
carbonate
surfactants in a blown powder, and 10% by weight sodium percarbonate (for
example,
see examples, sodium percarbonate sample 1 and 2) was placed, on a petri dish
with no
external barrier, in an incubator with controlled ambient conditions of
32°C and 80%
relative humidity. The detergent composition was exposed to these said
conditions in the
incubator for 24 hours.
The mean particle size is determined before and after the detergent
composition was
exposed to the said conditions. The mean particle size of the detergent
composition is
measured using the method ISO 3118 (1976), where 100g of product is used to
determine
the mean particle size, the sieve sizes that are used are 250, 425, 600, 850,
1180 and 2000
micrometers, and the time the product is allowed in the sieves before the mean
particle
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size is measured is 5 minutes. See example 1.
Bulk density
The granular detergent composition comprises a blown powder, a percarbonate
source,
and additional detergent ingredients, and has a bulk density less than 570g/1.
When the
detergent composition is stored in conditions of 32°C and 80% relative
humidity for 8
weeks, after storage in these conditions, the detergent composition has a bulk
density of
90% to 100% of the original bulk density.
For the purpose of this invention, this is determined by the following
l.5kg detergent composition comprising 20% by weight alkyl sulphate surfactant
in a
blown powder, less than 2% by weight other cationic or anionic surfactants in
a blown
powder, 25% by weight sodium tripolyphosphate in a blown powder, 6% by weight
1.6
ratio silicate in a blown powder, 15% by weight carbonate in a blown powder,
and 10%
by weight sodium percarbonate (for example, see examples, sodium percarbonate
example 1 and 2) was stored, in packaging typical of laundry detergent
products, in a
room with controlled ambient conditions of 32°C and 80% relative
humidity. The
detergent composition was stored in these said conditions for 8 weeks.
The bulk density is determined before and after the detergent composition was
stored in
these said conditions. The bulk density of the detergent composition is
measured using
the method ISO 3424 (1975), see example 2.
Other preferred components of the detergent composition
The detergent composition can comprise an alkali or earth metal salt of
phosphate. The
alkali or earth metal salt of phosphate can be any known in the art, or
combination
thereof. Preferably this is sodium phosphate or sodium tripolyphosphate. The
detergent
composition comprises less than 36%, preferably from 1 to 35%, more preferably
from
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10% to 35%, even more preferably from 12% to 30%, by weight an alkali or earth
metal
salt of phosphate. Detergent compositions containing a low level of, or no,
phosphate can
also be used by this invention. Typical sources of phosphate that can be
comprised by the
composition of the invention are described hereinafter.
The detergent composition is preferably a high sudsing detergent formulation.
These can
be any high sudsing detergent formulations known in the art, or part thereof.
The
detergent composition can comprise less than 5%, preferably less than 2%, more
preferably less than 1 % by weight a suds suppresser. The suds suppresser can
be any
known in the art, or combination thereof. Preferably the suds suppresser is
either a soap,
paraffin, wax, or any combination thereof. Also, the detergent composition can
comprise
less than 0.06% by weight extractable suds suppressing silicone. The
extractable suds
suppressing silicone can be any known in the art, or any combination thereof.
Typical
suds suppressers, including suds suppressing silicone are described
hereinafter.
The detergent composition has a moisture content of less than 10%, preferably
6% to 9%
by weight.
When used herein, 'moisture content' means for the purpose of the invention,
any free
water molecules present in the detergent composition or water molecules in the
form of
hydrates, such as present in sodium phosphate, usually this is sodium
tripolyphosphate.
The reserve alkalinity gives a measure of the buffering capacity of the
detergent. This is
the amount of NaOH or detergent composition required to neutralise 0.2M
hydrochloric
acid to pH 7.5. The granular detergent composition has a preferred reserve
alkalinity of at
least 6g NaOH per 100g detergent composition, measured to a pH of 7.5.
The detergent composition comprises 0.05% to 2%, preferably 0.1% to 2%, more
preferably 0.2% to 1.5%, even more preferably 0.5% to 1.0%, by weight a metal
chelating agent. The metal chelating agent can be any agent known in the art,
or
combination thereof, that chelates heavy metal ions, as described hereinafter.
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Bleaching-System
The granular detergent composition of the invention comprises a source of
percarbonate.
The percarbonate source acts as a source of available oxygen. Other sources of
available
oxygen can also be comprised by the detergent composition of the invention, to
form a
bleaching system. Typical bleaching systems comprised by the detergent
composition are
described hereinafter.
When used herein, 'bleaching system' means for the purpose of the invention
any
bleaching system known in the art that comprises the percarbonate source and
an
additional bleaching compound, preferably a peracid or precursor thereto.
Percarbonate Source
When used herein, 'percarbonate source' means for the purpose of the
invention, any
source of percarbonate, typically comprising a salt of percarbonate,
preferably the salt of
percarbonate is sodium percarbonate.
The detergent composition comprises a percarbonate source at a level of from
0.01 % to
12%, preferably from 2% to 10%, more preferably from 3% to 7%, by weight of
the
detergent composition.
The percarbonate source of the invention can be prepared by any method known
in the
art, preferably a fluidised bed process. The fluidised bed process can be any
known in the
art.
The percarbonate source preferably comprises less than 2%, preferably less
than 1.5%,
more preferably less than 1.2%, even more preferably less than 1 % by weight
chloride
ions, or chloride containing compounds.
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The detergent composition can comprise a coated source of percarbonate. The
source of
percarbonate can be coated by any coating known in the art, or combination
thereof.
Preferably, the coating comprises one or more alkali metal salt, preferably
this is sodium
carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, or any
combination
thereof. The coated sodium percarbonate is formed by contacting the
percarbonate source
with the coating in such a way that the coating is present on the surface of
the source of
percarbonate. The coating is present on the surface of the source of
percarbonate in such a
way as to either completely or partially coat the percarbonate source.
The coated source of percarbonate is prepared by a method comprising
contacting the
source of percarbonate with carbon dioxide to form a coating of sodium
bicarbonate on
the surface of the sodium percarbonate particle. Usually this is done in the
presence of
moisture.
The coated source of percarbonate particle comprises a coating present at a
level of
0.01 % to 20%, preferably 1 % to 15%, more preferably 4% to 10%, by weight of
the
coated sodium percarbonate particle Any detergent components which comprise
sodium
percarbonate can also be coated in this manner.
The coated percarbonate can be prepared by a fluidised bed process and/or by
spraying
the coating onto the surface of the sodium percarbonate.
The source of percarbonate preferably has a mean particle size of 500 to 1000,
preferably
500 to 850, more preferably 550 to 800 micrometers.
Additional detergent ingredients
The detergent composition typically comprises additional detergent
ingredients. These
detergent ingredients are described below. Preferably the detergent
composition
comprises a surfactant, builder, chelant and a bleaching system.
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~nrfactant~
Nonionic Alkoxylated Surfactant
Essentially any alkoxylated nonionic surfactants can also be comprised by the
composition of the invention. 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.
Highly preferred are nonionic alkoxylated alcohol surfactants, being the
condensation
products of aliphatic alcohols with from 1 to 75 moles of alkylene oxide, in
particular
about 50 or from 1 to 15 moles, preferably to 11 moles, particularly ethylene
oxide and/or
propylene oxide, are highly preferred nonionic surfactant comprised in the
anhydrous
component of the particles of the invention. 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 9 moles and in
particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
Nonionic Pol~ydroxy Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides are highly preferred nonionic surfactant
comprised by the
composition of the invention , in particular those having the structural
formula
R2CONR 1 Z wherein : R 1 is H, C 1 _ l g, preferably C,-C4 hydrocarbyl, 2-
hydroxy ethyl, 2-
hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable Cl-C4 alkyl,
more
preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is
a CS-C31
hydrocarbyl, preferably straight-chain CS-C19 or C~-C,9 alkyl or alkenyl, more
preferably straight-chain Cg-C 17 alkyl or alkenyl, most preferably straight-
chain C 11-
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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
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 highly preferred nonionic polyhydroxy fatty acid amide surfactant for use
herein is a
C 12-C 14 ~ a C 15-C 17 and/or C 16-C 1 g alkyl N-methyl glucamide.
It may be particularly preferred that the composition of the invention
comprises a mixture
of a C 12-C 1 g alkyl N-methyl glucamide and condensation products of an
alcohol having
an alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and
in
particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
The polyhydroxy fatty acid amide can be prepared by any suitable process. One
particularly preferred process is described in detail in WO 9206984. A product
comprising about 95% by weight polyhydroxy fatty acid amide, low levels of
undesired
impurities such as fatty acid esters and cyclic amides, and which is molten
typically
above about 80°C, can be made by this process.
Nonionic Fatt~Acid Amide Surfactant
Fatty acid amide surfactants or alkoxylated fatty acid amides can also be
comprised by
the composition of the invention. They include those having the formula:
R6CON(R7)
(R8 ) wherein R6 is an alkyl group containing from 7 to 21, preferably from 9
to 17
carbon or even 11 to 13 carbon atoms and R7 and R8 are each individually
selected from
the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -
(C2H40)xH,
where x is in the range of from 1 to 11, preferably 1 to 7, more preferably
form 1-5,
whereby it may be preferred that R7 is different to R8~ one having x being 1
or 2, one
having x being from 3 to 11 or preferably 5.
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Nonionic Alkyl Esters of Fatty Acid Surfactant
Alkyl esters of fatty acids can also be comprised in any material of the
invention. They
include those having the formula: R9C00(R10) wherein R9 is an alkyl group
containing
from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and
R10 is a
C1-C4 alkyl, C1-C4 hydroxyalkyl, or -(C2H40)xH, where x is in the range of
from 1 to
11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred
that R10 is a
methyl or ethyl group.
Nonionic Alkylpolysaccharide Surfactant
Alkylpolysaccharides can also be comprised by the composition of the
invention, such as
those disclosed in US Patent 4,565,647, Llenado, issued January 21, 1986,
having a
hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide,
e.g., a
polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to
18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The
glycosyl is
preferably derived from glucose.
Polyethylene/ Propylene Glycols
The composition of the invention may comprise polyethylene and/or propylene
glycol,
particularly those of molecular weight 1000-10000, more particularly 2000 to
8000 and
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most preferably about 4000.
Anionic Surfactant
The detergent composition of the 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
sulphate,
sulphonate, carboxylate and sarcosinate surfactants. Anionic sulphate
surfactants are
preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 1 g
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
Anionic Sulphate Surfactant
Anionic sulphate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulphates, alkyl ethoxysulphates, fatty oleoyl
glycerol
sulphates, alkyl phenol ethylene oxide ether sulphates, the CS-C 1 ~ acyl-N-(C
1-C4 alkyl)
and -N-(Cl-C2 hydroxyalkyl) glucamine sulphates, and sulphates of
alkylpolysaccharides
such as the sulphates of alkylpolyglucoside (the nonionic non-sulphated
compounds
being described herein).
Alkyl sulphate surfactants are preferably selected from the linear and
branched primary
Cg-C22 alkyl sulphates, more preferably the C 11-C 15 branched chain alkyl
sulphates and
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the C 12-C 14 linear chain alkyl sulphates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C l 0-C 1 g alkyl sulphates which have been ethoxylated with from 0.5 to 50
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a Cl 1-
C 1 g, most preferably C 11-C 15 alkyl sulphate which has been ethoxylated
with from 0.5
to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
Anionic Sulphonate Surfactant
Anionic sulphonate surfactants suitable for use herein include the salts of C5-
C2p linear
or branched alkylbenzene sulphonates, alkyl ester sulphonates, in particular
methyl ester
sulphonates, C6-C22 primary or secondary alkane sulphonates, C6-C24 olefin
sulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulphonates,
fatty acyl
glycerol sulphonates, fatty oleyl glycerol sulphonates, and any mixtures
thereof.
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Anionic Carboxylate Surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),
especially
certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to C 1 g alkyl group, x ranges from O to 10, and
the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is 0
is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate
surfactants
include those having the formula RO-(CHRI-CHR2-O)X-R3 wherein R is a C6 to Clg
alkyl group, x is from 1 to 25, Rl and R2 are selected from the group
consisting of
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl
unit connected to a secondary carbon. Preferred secondary soap surfactants 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-I-octanoic acid and 2-pentyl-I-heptanoic acid. Certain soaps may also be
included
as suds suppressers.
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-C 1 ~ linear or branched alkyl or alkenyl
group, Rl
is a CI-C4 alkyl group and M is an alkali metal ion. Preferred examples are
the myristyl
and oleoyl methyl sarcosinates in the form of their sodium salts.
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Cationic Surfactant
Another preferred optional ingredient of the detergent composition of the
invention, is a
cationic surfactant, which may preferably be present at a level of from 0.1 %
to 60% by
weight of the composition or particle, more preferably from 0.4% to 20%, most
preferably
from 0.5% to 5% by weight of the composition.
When present, 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 the stabilising agent is preferably from 1:30
to 20:1, more
preferably from 1:20 to 10:1.
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.
Cationic Mono-Alkoxylated Amine Surfactants
The optional cationic mono-alkoxylated amine surfactant for use herein, has
the general
formula:
R~ / AhR4
/N\ X
R3
R
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),
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methyl and ethyl, X- is an anion such as chloride, bromide, methylsulphate,
sulphate, 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:
R\ /(CH2CH20)1-SH
\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.
Cationic Bis-Alkoxylated Amine Surfactant
The cationic bis-alkoxylated amine surfactant for use herein, has the general
formula:
Ri / "YR3
N+
R2~ ~A,qR4
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
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atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11,
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, methylsulphate, sulphate, or the like, sufficient to provide
electrical neutrality.
A and A' can vary independently and are each selected from Cl-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:
+/CH2CH20H
X
CH / \CH2CH20H
3
wherein Rl is C6-C 1 g hydrocarbyl and mixtures thereof, preferably C6, Cg, C
l0, 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 Rl is derived from
(coconut) C12
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~ ~(CH2CH20)pH
N+ X
~(CH2CH20)qH
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wherein R 1 is C6-C 1 g hydrocarbyl, preferably C6-C 14 alkyl, independently p
is 1 to
about 3 and q is 1 to about 3, R2 is Cl-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.
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 l0-C 1 g alkyl dimethylamine oxide, and C 10-18
acylamido
alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be comprised by the composition of the
invention. These
surfactants can be broadly described as derivatives of secondary and tertiary
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amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
Betaine and sultaine surfactants are exemplary zwitterionic surfactants for
use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R
is a C6-Clg hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R2 is a
C1-CS
hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
Water-Soluble Builder Compound
The detergent composition of the invention preferably comprises a water-
soluble builder
compound, typically present at a level of from 0% to 36% by weight, preferably
from 1
to 35% by weight, more preferably from 10% to 35%, even more preferably from
12% to
30% by weight of the composition or particle. Preferably, the water-soluble
builder
compound is an alkali or earth alkali metal salt of phosphate present at the
level described
above.
Other typical water-soluble builder compounds include the water soluble
monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their
salts in which the polycarboxylic acid comprises at least two carboxylic
radicals
separated from each other by not more that two carbon atoms, borates,
phosphates, and
mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
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containing two carboxy groups include the water-soluble salts of succinic
acid, malonic
acid, (ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric
acid, tartronic
acid and fumaric acid, as well as the ether 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
Netherlands
Application 7205873, 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 US Patent No. 3,936,448, and the sulphonated
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
polymeta/phosphate in which the degree of polymerization ranges from about 6
to 21, and
salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
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The detergent composition of the invention, or any detergent component
comprised by
the detergent composition of the invention, may contain a partially soluble or
insoluble
builder compound.
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]. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106]~ 276 H20.
Preferred crystalline layered silicates for use herein have the general
formula:
NaMSix02x+l .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
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preferably 2. The most preferred material is 8-Na2Si205, available from
Hoechst AG as
NaSKS-6.
Organic Peroxyacid Bleaching System
The detergent composition of the invention preferably comprises an organic
peroxyacid
precursor. The production of the organic peroxyacid may occur by an in situ
reaction of
such a precursor with the percarbonate source. In an alternative preferred
execution a
preformed organic peroxyacid is incorporated directly into the composition.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as:
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is:
O
X-C-OOH
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
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EP-A-0170386.
Leaving Groups
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis reaction to occur within the optimum time frame (e.g., a wash
cycle).
However, if L is too reactive, this activator will be difficult to stabilize
for use in a
bleaching composition.
Preferred L groups are selected from the group consisting o~
Y R3 RsY
-O ~ , -O ~ Y , and -O
4
-N-C-R - ~ -N-C-CH R
R3 ~ R3 Y
I
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
> >
O Y O
CH2-C ~Cw
4
-p-C-R~ -N~C/NR4 , -N~C/NR
II II
O O
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R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group
containing from 1 to
14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4
is H or
R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be
substituted by
essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
The preferred solubilizing groups are -S03 M+, -C02 M+, -S04 M+, -N+(R3)4X and
O<--N(R3)3 and most preferably -S03 M+ and -C02 M+ wherein R3 is an alkyl
chain
containing from 1 to 4 carbon atoms, M is a canon which provides solubility to
the bleach
activator and X is an anion which provides solubility to the bleach activator.
Preferably,
M is an alkali metal, ammonium or substituted ammonium canon, with sodium and
potassium being most preferred, and X is a halide, hydroxide, methylsulphate
or acetate
anion.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Typical alkyl percarboxylic precursor compounds of the imide type include the
N-
,N,N 1 N 1 tetra acetylated alkylene diamines wherein the alkylene group
contains from 1
to 6 carbon atoms, particularly those compounds in which the alkylene group
contains 1,
2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred. The
TAED is preferably not present in the agglomerated particle of the present
invention, but
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preferably present in the detergent composition, comprising the particle.
Other alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl
hexanoyloxybenzene sulphonate (iso-NOBS), sodium nonanoyloxybenzene sulphonate
(NOBS), sodium acetoxybenzene sulphonate (ABS) and pentaacetyl glucose.
The detergent composition preferably comprises 0.1 % to 2%, preferably 0.1 %
to 1 %,
more preferably 0.2% to 0.7%, even more preferably 0.25% to 0.6%, by weight
TAED.
The detergent composition preferably comprises 0.1% to 4%, preferably 0.2% to
3%,
more preferably 0.4% to 2%, even more preferably 0.7% to 1.9%, by weight NOBS.
The detergent composition can also comprise a combination of NOBS and TAED,
present at the levels described hereinbefore.
Amide Substituted Alkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ CNR2CL R~ NCR2CL
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing
1 to 10
carbon atoms and L can be essentially any leaving group. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386.
Perbenzoic Acid Precursor
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Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable
O-acylated perbenzoic acid precursor compounds include the substituted and
unsubstituted benzoyl oxybenzene sulphonates, 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 ureas. Suitable imidazole type perbenzoic acid precursors include
N-benzoyl
imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing
perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine
and benzoyl
pyroglutamic acid.
Benzoxazin Organic Peroxyacid Precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example
in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
O
II
,,C
~N
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed Organic Peroxyacid
The organic peroxyacid bleaching system may contain a preformed organic
peroxyacid.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
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R~ CNR2COOH R~ -NCR2-COOH
O R5 O or R5 O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS is
H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide
substituted
organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc
acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid are also suitable herein.
Heavy Metal Ion Sequestrant
The detergent composition of the invention, or any detergent component
comprised by
the detergent composition of the invention, preferably comprise as an optional
detergent
ingredient, a heavy metal ion sequestrant. By heavy metal ion sequestrant it
is meant
herein components which act to sequester (chelate) heavy metal ions. These
components
may also have calcium and magnesium chelation capacity, but preferentially
they show
selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.05% to
2%,
preferably from 0.1% to 1.5%, more preferably from 0.25% to 1.2% and most
preferably
from 0.5% to 1% by weight of the composition.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates.
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Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine
tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine
pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric
acid, 2-
hydroxypropylenediamine disuccinic acid or any salts thereof. Especially
preferred is
ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline
earth metal,
ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-
hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-
hydroxypropyl-3-
sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
The (3-
alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-
monoacetic
acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also
suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes
suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859
describes a
suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-
phosphonobutane-
1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-disuccinic acid
(GADS),
ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-
disuccinic acid (HPDDS) are also suitable.
Enzyme
Another preferred optional detergent ingredient useful in the detergent
composition of the
invention, or any detergent component comprised by the detergent composition
of the
invention, is one or more additional enzymes.
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Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, esterases, cellulases,
pectinases,
lactases and peroxidases conventionally incorporated into detergent
compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by
Gist-
Brocades, those sold by Genencor International, and those sold under the
tradename
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated
into
the compositions in accordance with the invention at a level of from 0.0001 %
to 4%
active enzyme by weight of the composition.
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 tradename
Rapidase by
Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo
Industries A/S. Amylase enzyme may be incorporated into the composition in
accordance with the invention at a level of from 0.0001 % to 2% active enzyme
by weight
of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001% to
10% by weight of the particle, preferably 0.001% to 3% by weight of the
composition,
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., Thermomyces sp. or Pseudomonas sp. including
Pseudomonas pseudoalcali e~or Pseudomas fluorescens. Lipase from chemically or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is
derived from Pseudomonas pseudoalcali_~, which is described in Granted
European
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WO 01/36580 PCT/US00/30870
Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lams ig~nosa and expressing the gene in Asper~illus oryza, as host, as
described in
European Patent Application, EP-A-0258 068, which is commercially available
from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This
lipase is
also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7,
1989.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional detergent ingredients of
the
detergent composition of the invention, or any detergent component comprised
by the
detergent composition of the invention, and are preferably present as
components of any
particulate components where they may act such as to bind the particulate
component
together. By organic polymeric compound it is meant herein essentially any
polymeric
organic compound commonly used as dispersants, and anti-redeposition and soil
suspension agents in detergent compositions, including any of the high
molecular weight
organic polymeric compounds described as clay flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent
compositions of
the invention at a level of from 0.1 % to 50% by weight of the particle,
preferably from
0.5% to 25%, most preferably from 1% to 15% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids or their salts in which the polycarboxylic
acid
comprises at least two carboxyl radicals separated from each other by not more
than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of
such salts are polyacrylates of MWt 2000-5000 and their copolymers with
malefic
anhydride, such copolymers having a molecular weight of from 20,000 to
100,000,
especially 40,000 to 80,000.
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The polyamino compounds are useful herein including those derived from
aspartic acid
such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
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-~OCH2CH2)n N+CH2CH2-~CH2)a N+CH2CH20 }n X
b
(CH2CH20 ~ X (CH2CH20 )n X
wherein X is a nonionic group selected from the group consisting of H, C1-C4
alkyl or
hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20,
preferably
from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for
cationic
monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for
cationic
diamines (b=1), n is at least about 12 with a typical range of from about 12
to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-011965
and US 4,659,802 and US 4,664,848.
Suds Suppressing System
The detergent composition preferably comprises a suds suppresser at a level
less than 5%,
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preferably 0.01% to 5%, preferably from 0.05% to 4%, most preferably from 0.1%
to 3%,
by weight of the composition Preferably the suds suppresser is either a soap,
paraffin,
wax, or any combination thereof. If the suds suppresser is a suds suppressing
silicone,
then the detergent composition preferably comprises less than 0.06% by weight
extractable suds suppressing silicone.
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.
Preferably the composition comprises less than 0.6% by weight extractable suds
suppressing silicone.
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 suppresser typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably
12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as
sodium,
potassium, and lithium salts, and ammonium and alkanolammonium salts.
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Other suitable antifoam compounds include, for example, high molecular weight
fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic
C 1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to
hexa-
alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products
of cyanuric
chloride with two or three moles of a primary or secondary amine containing 1
to 24
carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-
alkali metal
(e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most
preferably a silicone antifoam compound comprising in combination:
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to
95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of
the antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
less
than 5%, preferably 0.01% to 5%, more preferably 0.05% to 4%, even more
preferably 0.1% to 3%, 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 less than 5%,
preferably
0.01% to 5%, more preferably 0.05% to 4%, even more preferably 0.1% to 3%, by
weight; a particularly preferred silicone glycol rake copolymer of this type
is
DC0544, commercially available from DOW Corning under the tradename
DC0544;
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(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 less than 5%, preferably 0.01% to 5%, more preferably 0.05%
to
4%, even more preferably 0.1% to 3%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and
comprises a silicone antifoam compound and an organic carrier material having
a melting
point in the range 50°C to 85°C, wherein the organic carrier
material comprises a
monoester of glycerol and a fatty acid having a carbon chain containing from
12 to 20
carbon atoms. EP-A-0210721 discloses other preferred particulate suds
suppressing
systems wherein the organic carrier material is a fatty acid or alcohol having
a carbon
chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a
melting point
of from 45°C to 80°C.
Clay Softening System
The detergent composition of the invention may comprise 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 composition of the invention 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,
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polyvinylpyrrolidonepolymers or combinations thereof.
al Polyamine N-oxide pol.
Polyamine N-oxide polymers suitable for use herein contain units having the
following
structure formula
P
(I)
R
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups or any
combination thereof whereto the nitrogen of the N-O group can be attached or
wherein
the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general
structures
O
1
O
(R1 ) x _N_(R2)Y 1
(R3)z or N_(R1 )x
wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or
CA 02388838 2002-04-24
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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 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 pyrridine, pyrrole, imidazole and
derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation.
The
degree of polymerisation is not critical provided the material has the desired
water-
solubility and dye-suspending power. Typically, the average molecular weight
is within
the range of 500 to 1000;000.
b) Copolymers of N-vinylpyrrolidone and N-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.
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c) Polyvinylpyrrolidone
The detergent composition of the invention may also utilize
polyvinylpyrrolidone
("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP Corporation, New
York, NY
and Montreal, Canada under the product names PVP K-15 (viscosity molecular
weight of
10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average
molecular
weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-
15 is
also available from ISP Corporation. Other suitable polyvinylpyrrolidones
which are
commercially available from BASF Cooperation include Sokalan HP 165 and
Sokalan
HP 12.
dl Polyvinyloxazolidone
The detergent composition of the invention may also utilize
polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average
molecular weight of from 2,500 to 400,000.
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e) Polyvinylimidazole
The detergent composition of the invention 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 hg tener
The detergent composition of the invention may also optionally comprise from
0.005% to
5% by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R1 R2
~N H H N
N D~Ij O C C 0 NOO N
rN H H NO
R2/ S03M S03M R~
wherein Rl 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, Rl 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 tradename Tinopal-LTNPA-GX by Ciba-
Geigy Corporation. Tinopal-LTNPA-GX is the preferred hydrophilic optical
brightener
useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and
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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)amino]2,2'-stilbenedisulfonic acid disodium
salt. This
particular brightener species is commercially marketed under the tradename
Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially
marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic Fabric Softening Agents
Cationic fabric softening agents can also be incorporated into the detergent
composition
of the invention or in compositions containing the detergent component 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.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5% to
15% by weight, normally from 1% to 5% by weight.
Other Optional Ingredients
Other optional detergent ingredients suitable for inclusion in the
compositions or
detergent component of the invention include highly preferably perfumes,
colours and
filler salts, with sodium sulphate being a preferred filler salt.
Form of Composition
The detergent composition of the invention can be made by a variety of
methods,
including dry-mixing, extruding, compacting and agglomerating of the various
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compounds comprised in the detergent composition. The particles can be present
in the
compositions as a separate component of the composition, or can be added to
other
components or compounds of the composition. The granular detergent composition
of the
invention can take a variety of physical forms including granular, flakes or
extrudate.
Laundry Washing Method
Laundry methods herein typically comprise treating soiled laundry with an
aqueous wash
solution for washing by machine or for washing by hand, having dissolved or
dispensed
therein an effective amount of a laundry composition. 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 1 to 65 litres, as are typical product dosages
and wash
solution volumes commonly employed in conventional laundry methods. Other
laundry
washing processes known in the art can also be used.
Packaging 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. A preferred packaging execution is
described in
European Application No. 94921505.7.
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Examples
Abbreviations used in examples
In the detergent compositions, the abbreviated component identifications have
the
following meaning:
LAS : Sodium linear C11-13 alkyl benzene sulfonate
LAS (I) : Potassium linear or branched C11-13 alkyl benzene
sulfonate
TAS : Sodium tallow alkyl sulfate
CxyAS : Sodium C 1 x - C 1 y alkyl sulfate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS : Sodium C 1 x-C 1 y alkyl sulfate condensed with
z moles of ethylene
oxide
CxyEz : Clx-Cly predominantly linear primary alcohol condensed
with an
average of z moles of ethylene oxide
QAS : R2.N+(CH3)2(C2H40H) with R2 = C 12 - C 14
QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11
APA : C8 - C10 amido propyl dimethyl amine
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of
tallow and coconut fatty acids
STS : Sodium toluene sulphonate
CFAA : C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA : C 16-C 18 alkyl N-methyl glucamide
TPKFA : C 12-C 14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(AlO2Si02)12.27H20 having a primary particle
size in the
range from 0.1 to 10 micrometers (weight expressed
on an
anhydrous basis)
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NaSKS-6 : Crystalline layered silicate of formula d- Na2Si205
Citric acid I : Anhydrous citric acid, 80% having a particle size of from 40
microns to 70 microns, and having a volume median particle size
of 55 microns
Citric acid II : Anhydrous or monohydrate citric acid, 80% having a particle
size
of from 15 microns to 40 microns, having a volume average
particle size of 25 microns
Malic acid : Anhydrous malic acid, 80% having a particle size of from 50
microns to 100 microns, having a volume median particle size of
75 microns
Malefic acid : Anhydrous malefic acid, 80% having a particle size of from 5
microns to 30 microns, having a volume median particle size of 15
microns
Tartaric acid : Anhydrous tartaric acid, 80% having a particle size of from 25
microns to 75 microns, having a volume median particle size of 50
microns
Carbonate I : Anydrous sodium carbonate having 80% by volume
of particles
with a particle size from 50 microns to 150
microns with a volume
median particle size of 100 microns
Carbonate II Anydrous sodium carbonate having 80% by volume
: of particles
with a particle size from 35 microns to 75
microns, having a
volume median particle size of 55 microns
Bicarbonate II: Anhydrous sodium bicarbonate having 80% by
volume of particles
with a particle size from 100 microns to 200
microns with a
volume median particle size of 150 microns
Bicarbonate I : Anydrous sodium bicarbonate having 80% by volume
of particles
with a particle size from 15 microns to 40
microns, having a
volume median particle size of 25 microns
Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1
)
Sulfate : Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
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Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a particle size
distribution between 425pm and 850pm
MA/AA : Copolymer of 1:4 maleie/acrylic acid, average molecular weight
about 70,000
MA/AA (1) : Copolymer of 4:6 maleic/acrylic acid, average molecular weight
about 10,000
AA : Sodium polyacrylate polymer of average molecular weight 4,500
CMC : Sodium carboxymethyl cellulose
Cellulose ether : Methyl cellulose ether with a degree of polymerization of
650
available from Shin Etsu Chemicals
Protease : Proteolytic enzyme, having 3.3% by weight of active enzyme, sold
by NOVO Industries A/S under the tradename Savinase
Protease I : Proteolytic enzyme, having 4% by weight of active enzyme, as
described in WO 95/10591, sold by Genencor Int. Inc.
Alcalase : Proteolytic enzyme, having 5.3% by weight of active enzyme, sold
by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight of active enzyme, sold
by NOVO Industries A/S under the tradename Carezyme
Amylase : Amylolytic enzyme, having 1.6% by weight of active enzyme, sold
by NOVO Industries A/S under the tradename Termamyl 120T
Lipase : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold
by NOVO Industries A/S under the tradename Lipolase
Lipase ( 1 ) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold
by NOVO Industries A/S under the tradename Lipolase Ultra
Endolase : Endoglucanase enzyme, having 1.5% by weight of active enzyme,
sold by NOVO Industries A/S
PB4 : Particle containing sodium perborate tetrahydrate of nominal
formula NaB02.3H2 O, the particles having a weight average
particle size of 950 microns, 85% particles having a particle size of
from 850 microns to 950 microns
PB 1 : Particle containing anhydrous sodium perborate bleach of nominal
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WO 01/36580 PCT/US00/30870
formula NaB02.H 202, the particles having a weight average
particle size of 800 microns, 85% particles having a particle size of
from 750 microns to 950 microns
Percarbonate : The sodium percarbonate source of the invention as described
hereinbefore (see detailed description of the invention,
percarbonate source)
Coated
percarbonate: The coated sodium percarbonate source of the invention, as
described hereinbefore (see detailed description of the invention,
percarbonate source), as described hereinafter, with 4.5% by
weight coating comprising sodium bicarbonate and/or sodium
sulphate and prepared by a fluidised bed process (percarbonate
sample 2) or with 4.5% by weight sodium carbonate and/or sodium
sulphate and prepared by a crystalline/classification process, ex
Solway
NOBS : Particle comprising nonanoyloxybenzene sulfonate in the form of
the sodium salt, the particles having a weight average particle size
of 750 microns to 900 microns
NAC-OBS : Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate,
the particles having a weight average particle size of from 825
microns to 875 microns
TAED I : Particle containing tetraacetylethylenediamine, the particles having
a weight average particle size of from 700 microns to 1000
microns
TAED II : Tetraacetylethylenediamine of a particle size from 150 microns to
600 microns
DTPA : Diethylene triamine pentaacetic acid
DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename bequest 2060
Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach ( 1 )
dextrin
soluble polymer
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Photoactivated : Sulfonated alumino phthlocyanine encapsulated in bleach (2)
dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
:
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-
:
yl)amino) stilbene-2:2'-disulfonate
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer
in the form of
its sodium salt.
HEDP : l,l-hydroxyethane diphosphonic acid
PEGx : Polyethylene glycol, with a molecular weight of
x (typically 4,000)
PEO : Polyethylene oxide, with an average molecular
weight of 50,000
TEPAE : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidosole, with an average molecular
weight of 20,000
PVP : Polyvinylpyrolidone polymer, with an average molecular
weight of
60,000
PVNO : Polyvinylpyridine N-oxide polymer, with an average
molecular
weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an
average molecular weight of 20,000
QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-(C2H4 O))n, wherein n = from 20 to
30
SRP 1 : Anionically end capped poly esters
SRP 2 y Diethoxylated poly (1, 2 propylene terephtalate)
short block
polymer
PEI : Polyethyleneimine with an average molecular weight
of 1800 and
an average ethoxylation degree of 7 ethyleneoxy
residues per
nitrogen
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
Opacifier : Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron 621
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Wax : Paraffin wax
Example 1
The mean particle size of the detergent composition was determined by the
method
described hereinbefore (see detailed description of the invention, mean
particle size).
A detergent composition used to determine the mean particle size (MPS) is
described
hereinbefore (see detailed description of the invention, mean particle size).
The mean
particle size of a detergent composition comprising 10% by weight sodium
perborate
monohydrate (sodium perborate sample) is also shown, along with two detergent
compositions comprising 10% by weight sodium percarbonate (sodium percarbonate
sample 1 and 2, see below for a more detailed description) before (Oh) and
after exposure
for 24 hours (24h) to conditions of 32°C and 80% relative humidity by
the method
described hereinbefore (see detailed description of the invention, mean
particle size).
The sodium percarbonate sample 1 comprises a coated sodium percarbonate
comprising
or with 4.5% by weight sodium carbonate and/or sodium sulphate and prepared by
a
crystalline/classification process, ex Solvay.
The sodium percarbonate sample 2 comprises a coated sodium percarbonate
comprising
4.5% by weight a coating comprising sodium bicarbonate and/or sodium sulphate
and the
coated sodium percarbonate is prepared by a fluidised bed process
Results
The particle size distribution(PSD)s of the said detergent compositions are
shown below.
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Particle Sodium Sodium percarbonate
Size perborate sample 1
sample
(Sieve PSD (Oh) PSD (24h) PSD (Oh) PSD (24h)
size)
2000 0 0.16 0.02 0.58
180 2.95 10.89 5.19 7.23
850 6.71 18.84 11.13 14.01
600 11.12 21.29 16.3 18.56
425 16.88 20.16 15.83 25.02
250 37.32 30.85 29.54 34.14
Pan 44.82 26.24 41.95 26.2
MPS (p,m) 311 473 346 437
Particle Sodium
Size percarbonate
sample
2
(Sieve PSD (Oh) PSD (24h)
size)
2000 0 0.01
180 4.45 3.98
850 9.31 9.52
600 19.6 20.92
425 16.75 21.73
250 28.62 37.89
Pan 41.02 32.67
MPS (pm) 351 386
PerboratePercarbonate Percarbonate
sample sample 1 sample 2
Time Oh 24h Oh 24h Oh 24h
MPS (gym) 387 593 456 540 452 467
Increase in MPS 206 84 S
(gym)
Increase in MPS
(% of original 52% 26% 10%
MPS)
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These data show that when selected sodium percarbonate, as opposed to sodium
perborate is comprised by a detergent composition, the detergent composition
has, after
being exposed simultaneously to 32°C and 80% relative humidity for 24
hours by the
method described hereinbefore (see detailed description of the invention, mean
particle
size), a mean particle size of 100% to 130% of the original mean particle
size.
Example 2
Perborate Percarbonate Percarbonate
sample sample 1 sample 2
wk0 wk8 wk0 wk8 wk0 wk8
Bulk density 485 423 475 436 475 446
(g/1)
Bulk density
(% of original)100 87 100 92 100 94
These data show that when selected sodium percarbonate, as opposed to sodium
perborate is comprised by a detergent composition, the detergent composition
has, after
being stored in conditions of 32°C and 80% relative humidity for 24
hours by the method
described hereinbefore (see detailed description of the invention, mean
particle size), a
bulk density of 90% to 100% of the original mean particle size.
Example 3
Table I
The following compositions are in accordance with the invention.
B C E F G H I
TPKFA 5 2 3 1
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LAS 3 20 1 15 20 2
QAS 2 10
C28E3S 3 2 S
C28E7 10 2 I 5 10
C68AS 20 15 10
TAS 15
ES 1 6 15
SADS 10 3 1
STPP 5 20 25 10 30 1 25
eolite A 5 10 I 6 16 15
Silicate 1 10 6 9 I 6 6
S
Carbonate 20 10 15 5 20 5
Dried carbonate 1 1 10
DTPA 0.4 1 0.3 2 0.1 2
Mg Sulfate 0.2 2 0.1
Citric Acid 6 5 2.5 3 8 0.1
MA/AA 0.8 0.9 1 0.2
MA/AA ( 1 ) 0.1 0.8
A 1 0.7
CM C 0.2 0.4 0.4 0.8
SRP 1 0.1 0.2
SRP2 0.2 0.1 0.2
Protease 0.1 0.6 0.8
Protease I 0.2 0.1 0.6
Cellulase 0.1 0.4 0.2
mylase 0:6 0.1 0.05
mylase II 0.2 0.6 0.1
Lipase 0.1 0.6 0.5
Lipase I 0.1 0.2
Endolase 0.6 0.2
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B1 1
OB S 2 1 0.5 1.5 2 1.5 3
AED 1 0.5 0.6 1.6 1 1
Percarbonate 3 12 1 1 2 3 1
Coated percarbonate12 12 3 7 6 7 5
Photoactivated 0.05 0.05
bleach 1
hotoactivated 0.05
bleach 2
Brightener 1 0.3 0.05 0.1
rightener 2 0.1 0.05 0:3
Silicone antifoam 0.2 0.1 0.05 0.05
Perfume 0.5 0.2 1
isc/minor o 0 0 0 0 0 0 0 0
100% 100% 100% 100% 100% 100% 100% 100%100%
Table II
The following compositions are in accordance with the invention._
K M O P Q
TPKFA 2
LAS 20 15 3 20 15 15 0 15
QAS 2 0.5
C28E3S
C28E7 2 1 20
C68AS 10
TAS 6 5
ES 8
SADS 3
STPP 35 25 5 15 20 5 30 10 15
eolite A 8 20
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Silicate 8 7 1.4 6 1.5 9 9 9
Carbonate 10 12 20 9 12 20 10 15 15
Dried carbonate 1 3 7
DTPA 0.9 0.5 1 1 0.3 0.5 0.4 0.8 0.9
Mg Sulfate 0.6 1.4 0.8 1.4 1.2 1
Citric Acid 10
A/AA 1 0.5 0.5 1 0.5 1 1.5 0.1
MA/AA ( 1 ) 0.6 0.75
A 1 0.5
CMC 0.5 0.4 0.8 1 0.4 0.2 0.4 0.4 0.3
SRP 1 0.3 0.1
SRP2 0.4 0.1
Protease 0.7 0.4 0.1 0.2 0.2 0.2 0.1
Protease I 0.2 0.1 0.0 0.4 0.3 0.6 0.1 0.7
5
Cellulase 0.1 0.2 0.05
mylase 0.1 0.1 0.6 0.6
mylase II 0.05 0.1 0.15 0.3
Lipase 0.2 0.1
Lipase I 0.
I
Endolase
B1
OB S 1.9 1.5 2 0.5 1.5 1.9 1 0.7
TAED 0.5 1.5 0.6
ercarbonate 3 2 2
Coated percarbonate 10 5 10 7 8 6 10
Photoactivated 0.01
bleach 1
Photoactivated 0.01
bleach 2
Brightener 1 0.05 0.05 0.050.05 0.05 0.1 0.05
Brightener 2 0.1 0.1 0.05 0.1 0.05
Silicone antifoam0.2 0.15 0.05 0.010.01
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erfume 0.2 0.4 0.3 0.1 0.6 0.4 0.2 0.4
5
MiscJminor to to to to o to o to to
100% 100%100% 100% 100% 100% 100% 100%100%
52
