Note: Descriptions are shown in the official language in which they were submitted.
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Foaming component
Technical Fieid
This invention relates to a foaming composition useful in any application
where foam
is required, such as cleaning compositions, pharmaceutical compositions, food
and
beverages.
Back~around to the Invention
Foam formation or sudsing is desired in various applications for different
reasons. In
detergents, specific surfactants are known to provide sudsing in the washing
water.
It can be desirable that the foaming or sudsing occurs readily and that the
foaming or
sudsing has the desired duration. For example, it can be desirable that the
effervescence, suds or foam occurs immediately upon contact with water, and
that it
is stable or continues during use.
Furthermore, to maximise the foaming, sudsing or effervescence capacity of
these
techniques in use upon contact with water, such contact with water or moisture
should be avoided during manufacturing or storage.
Components which react together upon contact with water to produce
effervescence
' - are known detergent ingredients. For example, WO 92/18596 discloses
detergents
comprising admixed citric acid and sodium carbonate salt as an aid to improve
the
detergent solubility. Effervescence systems are also widely known in
pharmaceutical
or agricultural applications, for example as described in GB-A-2,184,946.
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The inventors have now found that an effervescence component capable of
providing
a gas, can be used to produce foaming or sudsing, when used in a specific
combination with a surface active component capable of reducing the surface
tension,
so that controlled, rapid, improved sudsing and/ or foaming is achieved. Upon
contact with water, the components comprising the specific effervescence
component
and the specific surface active component, chemically forms microbubbles,
preferably
having an average diameter of 200 microns or less. The inventors have found
that the
formation of these microbubbles enables an improved control of the sudsing or
foaming or effervescence, and that it results in improved foaming or sudsing
stability.
e.g. rapidly formed arid stable or long-lasting foam or suds can be obtained.
Also, it has been found that the components of the invention provide improved
effervescence and dispensing and dissolving of the component or the product
comprising the component.
Furthermore, it has been found that these components are very stable upon
storage.
Summary of the Invention
The invention provides a substantially anhydrous foaming component capable of
providing foaming or sudsing without agitation, comprising intimately mixed, a
substantially anhydrous surface active component capable of reducing the air-
water
surface tension, and an effervescence component capable of formation of a gas
upon
contact with water.
The component or mixtures of different foaming component according to the
invention may be used in any application where a method for providing sudsing,
foaming or ei~ervescence is useful. In particular, the composition may be used
in,
preferably solid, cleaning compositions, pharTrraceutical products, cosmetic
products
and solid food or beverage products and the component may be in usefixl in
applications where no agitation or limited agitation is possible or required,
such as
hand wash detergent compositions and soaking compositions.
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Detailed descri,~tion of the invention
The foaming component of the invention is capable of providing foaming or
sudsing
without agitation. It should be understood that for the purpose of the
invention, when
used herein 'foaming' means any form of formation of gas bubbles, includes
sudsing
and effervescing. It should be understood that for the purpose of the
invention
agitation may be desirable.
The foaming component of the invention and the surface active component and
preferably the effervescence component are substantially anhydrous.
When used herein, 'substantially anhydrous' means that no more than 5% by
weight
of free moisture is present, preferably no more than 4%, even more preferably
no
more than 3% and most preferably no more than 2% or even 1% by weight. The
free
moisture content as used herein, can be determined by placing 5 grams of the
substantially anhydrous component in a petri dish and placing this petri dish
in a
convection oven at 50°C for 2 hours, and subsequently measuring the
weight loss,
due to water evaporation.
The effervescence component and the surface active component are intimately
mixed.
When used herein, 'intimately mixing/ mixed' or 'intimate mixture' means for
the
purpose of the invention that components of the foaming component are
substantially
homogeneously divided in the foaming component.
The intimate mixture of the components of the foaming component of the
invention
can be obtained by any process involving the mixing of the components, which
can
be part of a tableting process, extrusion process and agglomeration processes.
Preferably, the particle is prepared by a process whereby a melt of the
surface active
component is admixed to the effervescence component, whereafter the mixture is
solidified to form the foaming component, preferably by solidifying the melt,
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preferably by reducing the process temperature. When the effervescence
component
comprises more than one component, the components are preferably premixed.
When additional components are to be incorporated in the component, the melt
of the
surface active component is preferably admixed to the additional ingredients
and
effervescence component, which are preferably premixed prior to admixed the
melt,
to obtain an intimate mixture of the components prior to addition of the melt.
Preferably, the foaming component of the invention comprises the effervescence
component and the surface active component such that upon contact with water,
chemically microbubbIes of gas are produced which have an average diameter
size of
400 microns or less, preferably 200 microns or less, more preferably 150
microns or
less, more preferably 100 microns or less or even 50 microns or less, which
can be
achieved by intimately mixing the components.
The foaming component or the compositions containing the component can also
comprise additional ingredients, as described herein. The precise nature of
these
additional ingredients, and levels of incorporation thereof will depend on the
application of the component or compositions and the physical form of the
components and the compositions.
The component preferably comprises the surface active component at a level of
from
1% to 95%, more preferably from 10% to 70%, even more preferably from 20% to
60% or even to 50% by weight of the composition. The composition preferably
comprises the effervescence component at a level of from 5% to 99%, more
preferably from 10% to 90%, even more preferably from 15% to 60% by weight of
the composition.
The weight ratio of the surface active component to the effervescence
component, or
when present, to the acid source therein, is preferably from 20:1 to 1:10,
more
preferably 9:1 to 1:9, more preferably from 5:1 to 1:8, more preferably from
4:1 to
1:4.
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The component, when in the form of a particle or comprised in a particle, is
preferably such that 80% by weight of the particles has an particle size of
more than
75 microns (more than 80% by weight of the particles on Tyler sieve mesh 200)
and
less than 10% by weight of the particles has a particle size of more than 2
cm;
preferably 80% by weight of the particles has an particle size of more than
150
microns (80% by weight on Tyler sieve mesh 100) and less than 10% by weight of
the particles has a particle size of more than 1 cm; or more preferably 80% by
weight
of the particles has an particle size of more than 300 nucrons (80% by weight
on
Tyler sieve mesh 48) and less than 10% by weight of the particles has a
particle size
of more than to 0.5 cm; or even more preferably the particles have an average
particle
size of from 500 microns (on Tyler sieve mesh 32) to 3000 microns, more
preferably
from 710 microns (on Tyler mesh sieve24) to 1180 microns (through Tyler mesh
sieve 14).
Preferably, the density of the component is from 500 g/litre to 1200 g/litre,
more
preferably from 650 g/litre to 900g~litre.
The component of the invention is particularly useful in nonaqueous liquid
compositions or solid compositions, preferably cleaning products or food or
beverage
products. The component may be present as a separate particle or the it can be
present as a part of a component of the solid or nonaqueous liquid
composition. The
solid cleaning compositions are preferably solid laundry or dish washing
compositions, preferably in the form of flakes or pastilles, more preferably
in the form
of granules or extrudates or tablets, preferably having a density of at least
SOOg/litre,
more preferably at least 700g/litre.
Effervescence component
Any effervescence system capable of forming a gas upon contact with water,
known
in the art, can be used as effervescence component in the foaming component of
the
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invention. A preferred effervescence component comprises an acid source,
capable of
reacting with an alkali source in the presence of water to produce a gas.
The alkali source or part thereof is preferably a components of the
effervescence
component, when an acid source is present.
The acid source may be any organic, mineral or inorganic acid, or a derivative
thereof, or a mixture thereof. Preferably the acid source comprises an organic
acid.
The acid source is preferably substantially anhydrous or non-hygroscopic and
the acid
is preferably water-soluble. It may be preferred that the acid source is
overdried.
Suitable acids source components include citric, malic, maleie, fumaric
aspartic,
glutaryc, tartaric succinic or adipic acid, monosodium phosphate, boric acid,
or
derivative thereof. Citric acid, maieic or malic acid are especially
preferred.
Most preferably, the acid source provides acidic compounds which have an
average
particle size in the range of from about 75 microns to 1180 microns, more
preferably
froml SO microns to about 710 microns, calculated by sieving a sample of the
source
of acidity on a series of Tyler sieves.
The effervescence component preferably comprises an alkali source. Any alkali
source which has the capacity to react with the acid source to produce a gas
may be
present in the particle, including sources capable of producing nitrogen,
oxygen or
carbondioxide gas. Preferred can be perhydrate bleaches and silicate material.
The
alkali source is preferably substantially anhydrous or non-hydroscopic. It may
be
preferred that the alkali source is overdried.
Preferably the produced gas is carbon dioxide, and therefore the alkali source
is a
preferably a source of carbonate; in a preferred embodiment, the alkali source
is a
carbonate salt. Examples of preferred carbonates are the alkaline earth and
alkali
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metal carbonates, including sodium or potassium 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 i5,
1973. Alkali metal percarbonate salts are also suitable sources of carbonate
species,
which may be present combined with one or more other carbonate sources.
The carbonate and bicarbonate preferably have an amorphous structure. The
carbonate and/ or bicarbonates may be coated with coating materials. The
particles
of carbonate and bicarbonate can have a mean particle size of 75 microns or
greater,
preferably 150~m or greater, more preferably of 250~m or greater, preferably
SOO~m
or greater. It may be preferred that the carbonate salt is such that fewer
than 20% (by
weight) of the particles have a particle size below SOO~m, calculated by
sieving a
sample of the carbonate or bicarbonate on a series of Tyler sieves.
Alternatively or in
addition to the previous carbonate salt, it may be preferred that the fewer
than 60%
or even 25% of the particles have a particle size below 1501tm, whilst fewer
than 5%
has a particle size of more than 1.18 mm, more preferably fewer than 20% have
a
particle size of more than 212 Vim, calculated by sieving a sample of the
carbonate or
bicarbonate on a series of Tyler sieves.
The molecular ratio of the acid source to the alkali source present in the
particle core
is preferably from 60;1 to 1:60, more preferably from 20:1 to 1:20, more
preferably
from 10:1 to 1:10, more preferably from 5:1 to 1:3, more preferably from 3:1
to 1:2,
more preferably from 2:1 to 1:2.
Surface active component
The foaming component of the invention may comprise any surface active
component
known in the art, which reduces the water-air surface tension. Which surface
active
component is preferably incorporated in the composition of the invention, will
depend
on the application of the component of the invention, and the physical form
thereof.
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The surface active component can comprise one or more compounds. Preferably,
the
component comprises compounds which are, at least partially, water-soluble.
Preferably, the component is anhydrous.
The surface active component preferably has a melting point above
30°C, more
preferably above 45°C, more preferably above 50°C, and it may be
preferred that the
surface active component has a melting point above 80°C, in
particularly to ensure
that the surface active component is solid under normal storage conditions,
whilst
readily forming a melt above the preferred melting point, depending on the
application of the composition of the invention.
It may be preferred that the surface active component comprises one or more
nonionic components or one or more anionic components or mixtures thereof .
In particular when the component of the invention is for use in cleaning
compositions, the surface active component preferably comprises one or more
components, selected from the group comprising alkyl sulfate surfactants and
alkyl
sulphonate surfactants, as described herein and in particular alkoxylated
alcohols, - -
including polyethylene and/or propylene glycols, alkoxylated fatty acid amides
and
alkoxylated alcoholamides, including ethanolamides and specific nonionic
surfactants,
including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants,
alkyl
esters of fatty acids and specific alkylpolysaccherides surfactant or mixtures
of any of
these nonionics compounds and anionic compounds, as described herein.
Thus, preferably, one or more of the components comprised in the foaming
component are detergent actives which can contribute to the cleaning
performance of
the particle or the cleaning composition comprising the particle. Highly
preferred
substantially anhydrous surface active components suitable in the foaming
component
of the invention, are one or more nonionic surfactant, selected from the group
of
nonionic alkoxylated surfactants, including alkoxylated alcohol surfactants,
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polyhydroxyfattyacid amide surfactants, (alkoxylated) fatty acid amide
surfactants
and alkylpolysaccharide surfactants, or mixtures thereof, as described herein
after.
In a highly preferred aspect of the invention, the surface active component
comprises a mixture of polyhydroxy fatty acid amides and/ or polyethylene
glycols,
and/ or alkoxylated fatty acid amides and/ or condensation products of
aliphatic
alcohols with from 1 to 11 moles of alkylene oxide, as described in more
detail
below. When present, the ratio of the polyhydroxy fatty acid amides to the
condensation products of aliphatic alcohols is preferably from 20:1 to 1:20,
more
preferably from 10:1 to 1:10, more preferably from 8:1 to 1:8, more preferably
from
6:1 to 1:6, most preferably from 2:1 to 1:3. When present, the ratio of the
polyhydroxy fatty acid amides to the polyethylene glycol is preferably from
20:1 to
1:8, more preferably from 15:1 to 1:3, more preferably from i2:1 to 1:1, more
preferably from 10:1 to 1:1. When present, the ratio of the polyhydroxy fatty
acid
amides to the alkoxylated fatty acid amides is preferably from 20:1 to 1:20,
more
preferably from 15:1 to 1:10, more preferably from 10:1 to 1:10.
Nonionic alkoxylated surfactant
Essentially any alkoxyiated nonionic surfactants can also be comprised in the
surface
active component of the foaming component 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, up to 50 moles, preferably 1
to 1 S
moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide,
are
highly preferred nonionic surfactant comprised in the anhydrous component of
the
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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 S moles, of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides are highly preferred nonionic surfactant
comprised in
the surface active component of the foaming component of the invention , in
particular those having the structural formula R2CONR1Z wherein : R1 is H,
C1_18
preferably C,-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy,
propoxy,
or a mixture thereof, preferable C 1-C4 alkyl, more preferably C 1 or C2
alkyl, most
preferably C1 alkyl (i.e., methyl); and R2 is a CS-C31 hydrocarbyl, preferably
straight-chain CS-C 19 or C~-C,9 alkyl or alkenyl, more preferably straight-
chain C9-
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 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 surface active component comprises a
mixture of a C 12-C 1 g alkyl N-methyl glucamide and a condensation products
of a
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
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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 fatty acid amide surfactant
Fatty acid amide surfactants or alkoxylated fatty acid amides can also be
comprised in
the anhydrous material of the particle 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 12 to 14 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 a smaller alkoxylation number than the other-
Nonionic alkyl esters of fatty acid urfactant
Alkyl esters of fatty acids can also be comprised in the anhydrous material of
the
particle 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 R1~ 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 alk~l~olysaccharide surfactant
Alkylpolysaccharides can also be comprised in the surface active component of
the
foaming compoennt of the invention, such as those disclosed in U.S. Patent
4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group
containing
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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/ prop 1~g13rcols
A component of the surface active component may be a polyethylene oand/or
propylene glycol, particularly those of molecular weight 1000-10000, more
particularly 2000 to 8000 and most preferably about 4000.
Anionic surfactant
The surface active component of the composition of the invention may 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-aryl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18
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monoesters) diesters of sulfosuccinate (especiaiiy 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.
The anionic surfactant may preferably be present at a level of 1% to 90% by
weight
of the foaming component, preferably at a level of from 5% to 60%, and
preferably
of from 8% to 50% by weight of the component.
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 1 p-C 18 alkyl sulfates which have been ethoxylated with from 0. 5 to 50
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.
Anionic sulfonate surfactant
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Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20
linear or branched alkylbenzene sulfonates, alkyl ester sulfonates, in
particular methyl
ester sulphonates, C6-C22 primary or secondary alkane sulfonates, C6-C24
olefin
sulfonates, suifonated polycarboxyIic acids, alkyl glycerol sulfonates, fatty
aryl
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, R I 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
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Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(R 1 ) CH2 COOM, wherein R is a CS-C 1 ~ linear or branched alkyl or alkenyl
group,
Rl 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
A cationic surfactant may be comprised in the surface active component of the
composition of the invention, preferably be present at a level of from 0.5% to
80%
by weight of the component, more preferably from 1% to 60%, most preferably
from
3% to 50% by weight of the component.
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-alkoxvlated amine surfactants -
The optional cationic mono-alkoxylated amine surfactant for use herein, has
the
general formula:
Rl /ApRa
~N+ X_
R2~ ~R3
wherein Rl is an alkyl or alkenyi moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about i 6 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,
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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 1 S, most preferably 1 to about 8.
Highly preferred cationic mono-alkoxylated amine surfactants for use herein
are of
the formula
Ri /(CH2CH20)1-S H
~N+/ XO
CH3/ 'CH3
wherein R1 is C6-C 1 g hydrocarbyl and mixtures thereof, preferably C6-C 14,
especially C6-C I 1 alkyl, preferably Cg and C l0 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 (EO) 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-alkoxvlated amine surfactant
The cationic bis-alkoxylated amine surfactant for use herein, has the general
formula:
R~ /ApR3
N+ X
R2~ ~A,qR4
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
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
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17
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\ /CH2CH20H
N+ XO
CH / \CH2CH20H
3
wherein R1 is C6-C 1 g hydrocarbyl and mixtures thereof, preferably C6, 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 ~ 4 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~ ~(CHZCH20~H
N+ X-
R2~ ~(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 (EO) 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.
Am~hoteric 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 I O-C 1 g
alkyl
dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TN)7 C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be comprised in the surface active component
of the
composition of the invention or the compositions containing the particle of
the
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inve~ion. These surfactants can be broadly described as derivatives of
secondary.
and tertiary amines, derivatives of heterocyclic secondary and tertiary
amines, or
derivatives of quaternary ammonium, quaternary phosphonium or tertiary
sulfonium
compounds. Betaine and sultaine surfactants are exemplary zwitterionic
surfactants
for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R is a C6-C 1 g hydrocarbyl group, each R1 is typically C 1-C3 alkyl,
and R2
is a C1-CS hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio
hexanoate and the C l p_ 18 acylamidopropane {or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
leaning compositions
The foaming component of the invention can be incorporated in a cleaning
composition, preferably a solid composition, preferably granular, preferably
laundry
or dish washing compositions. The composition of the invention is then
preferably in
the form of a particle or comprised in a particle. _.
Then, the components of the invention for use in cleaning compositions, and/
or the
cleaning compositions preferably contain one or more additional detergent
components selected from additional surfactants, bleaches, builders, cheiants,
(additional) alkalinity sources, organic polymeric compounds, enzymes, suds
suppressors, lime soap dispersants, brighteners, soil suspension and anti-
redeposition
agents and corrosion inhibitors.
Highly preferred additional detersive actives or ingredients are cationic and
anionic
surfactants, as described above, suds suppressing systems, brighteners, and
bleaching
compounds, including perhydrate bleaches but preferably bleach activators, as
described hereinafter.
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Suds suppressing system
The foaming component of the invention provide a very rapid formation of very
stable foam.
However, it may be preferred that the foaming is limited or reduced at a
certain
moment during the washing process, for example to improve the drainage of the
suds
or foam from the washing process or the machine. Also, it may be preferred
that the
foaming is limited to the start of the contact with water (e.g. the beginning
of the
washing process), to provide effervescence, or improved dispensing or
dissolving of
the component or the product comprising the component. Therefore, it may be
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 or the component.
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 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.
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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 sans
thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to
24
carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the
alkali
metal salts such as sodium, potassium, and lithium salts, and ammonium and
alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohois, aliphatic
C 1 g-C4p 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) poiydimethyl siloxane, at a level of from 50% to 99%, preferably 75%
to 95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight
of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from 5%
to 50%, preferably 10% to 40% by weight;
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(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 copolymer of this type is DC0544, commercially available from DOW
Corning under the tradename DC0544;
(c) an inert Garner fluid compound, most preferably comprising a C16-C18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731
and comprises a silicone antifoam compound and an organic Garner 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.
Water-soluble builder compound
The foaming component of the invention or the cleaning compositions 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 or component.
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
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separated from each other by not more that two carbon atoms, borates,
phosphates,
and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing
two carboxy groups include the water-soluble salts of succinic acid, malonic
acid,
(ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid
and fumaric acid, as well as the ether 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
suifo substituents include the sulfosuccinate derivatives disclosed in British
Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the
sulfonated
pyrolysed citrates described in British Patent No. 1,439,000. Preferred
polycarboxylates are hydroxycarboxylates containing up to three carboxy groups
per
molecule, more particularly citrates.
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Borate builders, .as well as builders containing borate-forming materials that
can
produce borate under detergent storage or wash conditions are useful water-
soluble
builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium polymeta/phosphate in which the degree of polymerization ranges from
about
6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound
The component of the invention or the compositions containing the component of
the invention may contain a partially soluble or insoluble builder compound,
typically .
present at a level offrom 1% to 80% by weight, preferably from 10% to 70% by
weight, most preferably from 20% to 60% weight of the composition or component
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 IZ [~~2) 12 (5102)12]. X20
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wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
W02)86~S~02)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.
Perhydrate bleaches
An preferred additional components of the foaming component of the invention
or
the cleaning composition is a perhydrate bleach, such as metal perborates,
metal
percarbonates, particularly the sodium salts. Perborate can be mono or tetra
hydrated. Sodium percarbonate has the formula corresponding to 2Na2C03.3H202,
and is available commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic
perhydrate salt of use in the detergent compositions or foaming components.
Organic peroxyacid bleaching system
A preferred feature of the component of the invention or the cleaning
compositions
containing the foaming component of the invention, is an organic peroxyacid
bleaching system. In one preferred execution the bleaching system contains a
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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
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in
a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is
O
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of
from 0.5% to 6% by weight, more preferably from I% to 40 by weight, most
preferably from I .5% to 25 by weight of the compositions or component
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or
O-aryl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated
derivatives of
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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 oup_s
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis reaction to occur within the optimum time frame (e.g., a wash
cycle).
However, if L is too reactive, this activator will be difficult to stabilize
for use in a
bleaching composition.
Preferred L groups are selected from the group consisting of
Y R3 RsY
-p ~ ~ -O ~ Y , and
-N-C-R -N N -N-C-CH-R
Ra , ~ , Rs Y ,
I
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O
II
O C H2-C~
-p-C-Rt -NwC/NRa ,
. ' II
0
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3
R O Y
-O-C=C HR4 , and -N-S-C H-R4
R3 O
and mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group
containing from i
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 ofRl, R3 and R4 may be
substituted by essentially any functional group including, for example alkyl,
hydroxy,
alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium
groups.
The preferred solubilizing groups are -S03-M+, -COZ-M+, -S04-M+, -N+(R3)4X-
and O<--N(R3)3 and most preferably -S03 M+ and -C02-M+ wherein R3 is an alkyl
chain containing from 1 to 4 carbon atoms, M is a cation which provides
solubility to
the bleach activator and X is an anion which provides solubility to the bleach
activator. Preferably, M is an alkali metal, ammonium or substituted ammonium
cation, with sodium and potassium being most preferred, and X is a halide,
hydroxide, methylsulfate or acetate anion.
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.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains
from
1 to 6 carbon atoms, particularly those compounds in which the alkylene group
contains l, 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 preferably present in the detergent
composition,
comprising the particle.
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Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyioxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxvacid precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including those of the following general formulae:
R~ -C-N-R2-C-L R~ -N-C-R2-C-L
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, RZ is an alkylene
group containing from 1 to 14 carbon atoms, and RS is H or an alkyl group
containing I to 10 carbon atoms and L can be essentially any leaving group.
Amide
substituted bleach activator compounds of this type are described in EP-A-
0170386.
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted and
unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of
sorbitol, glucose, and all saccharides with benzoylating agents, and those of
the imide
type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-
benzoyl substituted 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.
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Cationic peroxyacid precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid
part of a suitable peroxyacid precursor compound with a positively charged
functional group, such as an ammonium or alkyl ammmonium group, preferably an
ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically
present in the solid detergent compositions as a salt with a suitable anion,
such as a
halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as
described
hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl
percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK
Patent
Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650,
08/298904 and 08!298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred
cationic peroxyacid precursors of the N-acylated caprolactam class include the
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trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium
methylene alkyl caprolactams.
Benzoxazin organic peroxvacid 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
CEO
C-R~
,N
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed organic geroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic peroxyacid , typically at a level of from 1 % to 15% by weight, more
preferably from 1% to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the following general formulae:
R~ C-N-R2-C-OOH
O R~ O or
R~ -N-C-R2-C-OOH
R5 01 10
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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 component of the invention or the cleaning compositions containing the
component of the invention preferably contain as an optional component a heavy
metal ion sequestrant. By heavy metal ion sequestrant it is meant herein
components
which act to sequester (chelate) heavy metal ions. These components may also
have
calcium and magnesium cheiation capacity, but preferentially they show
selectivity to
binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 20%,
preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most
preferably from 0.5% to S% by weight of the compositions or component
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 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.
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Enzyme
Another preferred ingredient useful in the component of the invention or the
cleaning
compositions containing the component of the invention is one or more
additional
enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, esterases, cellulases,
pectinases,
lactases and peroxidases conventionally incorporated into detergent
compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries
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 20% of active enzyme by weight of the composition or component
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 12% by weight, preferably 0.001 % to 10% by weight of the component, and
most
preferably from 0.001% to 03% by weight of the compositions.
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The lipase may be fungal or bacterial in origin being obtained, for example,
from a
lipase producing strain of icol sp., ThermomXces sp. or Pseudomonas sp.
including Pseudomonas gseudo lcaligenes or Pseudom~,g liluorescens. Lipase
from
chemically or genetically modified mutants of these strains are also useful
herein. A
preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is
described
in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanuginosa and expressing the gene in As~ergillus 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 components of the foaming
component of the invention or the cleaning compositions containing the
component
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 60%, preferably from 0.5% to 25%,
most
preferably from I% to 15% by weight of the compositions or compoennt.
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
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36
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 maieic anhydride, such copolymers having a molecular weight of from
20,000 to
100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic
acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, 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:
IH CH
X-(-OCH2CH2)n N+-CH2-CH2-(-CH2)a N+-CH CH O~X
b ~ 2 2
(CH2CH20 ~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
cationic diamines (b=1), n is at least about 12 with a typical range of from
about 12
to about 42.
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Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-
011965 and US 4,659,802 and US 4,664,848.
Clav softening_syst~m
The foaming component or the cleaning 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 dare transfer inhibiting agents
The foaming component or the cleaning compositions herein may also comprise
from
0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye
transfer
inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
a Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
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38
P
(I)
R
wherein P is a polymerisable unit, and
O 0 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
0
O
(R~ ) x - ~ -(R2)Y
(R3)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,
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39
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 poiyamine N-oxides having the general formula (I) wherein R is
an
aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O
functional
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) Conolvmers of N-vinvlpvrrolidone and N-vinvlimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone
having an
average molecular weight range of from 5,000 to 50,000. The preferred
copolymers
have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
c7 Polvvinvlovrrolidone
The components or the compositions herein may also utilize
polyvinylpyrrolidone
("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP Corporation, New
York,
NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular
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weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60
(average molecular weight of 160,000), and PVP K-90 (average molecular weight
of
360,000). PVP K-IS is also available from ISP Corporation. Other suitable
polyvinylpyrrolidones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HI' 12.
d) Polyvinyloxazolidone
The 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.
el Polyvin~rlimidazole
The compositions herein may also utilize poiyvinylimidazole as polymeric dye
transfer
inhibiting agent. Said polyvinylimidazoles preferably have an average
molecular
weight of from 2,500 to 400,000.
Optical bri htg ener
The foaming component or cleaning 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:
R~ R2
N H H N
N N C C ~ N--CO N
R2 S03M S03M Rl
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41
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, RI is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-
s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-UNPA-
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, Rl 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)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 sottening_agents
Cationic fabric softening agents can also be incorporated into the component
of the
invention or in compositions containing the component in accordance with the
present invention. Suitable cationic fabric softening agents include the water
insoluble
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42
tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276
and
EP-B-0 01 I 340.
Cationic fabric softening agents are typically incorporated at total levels of
from
0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ingredients
Other optional ingredients suitable for inclusion in the compoennt of the
invention or
the cleaning compositions herein of include highly preferably perfumes, bleach
catalysts, colours and filler salts, with sodium sulfate being a preferred
filler salt.
pH of the compositions
The present foaming component or the cleaning compositions can have an acidic,
neutral or an alkaline pH, depending on the application or the additional
ingredients
comprised in the component or composition. Preferably, the component or the
compositions herein have a pH measured as a 1 % solution in distilled water,
of from
3 to 13.5, preferably least 4.0, preferably from to I2.5, most preferably from
5 to
12Ø
Form of the cleanin compositions
The cleaning compositions, comprising the component, can be made via a variety
of
methods, including dry-mixing, extruding, compressing and agglomerating of the
various components comprised in the detergent composition. The foaming
component of the invention can be present in the cleaning compositions as a
separate
component of the composition, or can be part of or added to other components
or
compounds of the compositions.
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The cleaning compositions can take a variety of physical forms including
granular,
extrudates tablet or bar forms. The cleaning compositions are particularly the
so-
called concentrated granular detergent compositions adapted to be added to a
washing machine by means of a dispensing drawer or 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 cleaning
compositions
containing the foaming composition in accordance with the invention can be
from 0.1
mm to 5.0 mm, but it should preferably be such that no more that 5% of
particles are
greater than 2.Smm in diameter, or even l.7mm and that not more than 5% of
particles are less than 0. l5mm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the
composition into a number of fractions (typically 5 fractions) on a series of
Tyler
sieves. The weight fractions thereby obtained are plotted against the aperture
size of
the sieves. The mean particle size is taken to be the aperture size through
which 50%
by weight of the sample would pass.
The bulk density of granular cleaning or detergent compositions containing the
particulate composition in accordance with the present invention typically
have a bulk
density of at least 300 g/litre, more preferably from 500 g/litre or even
650g/litre to
1200 gllitre, more preferably to 850 g/litre. Bulk density is measured by
means of a
simple firnnel and cup device consisting of a conical funnel moulded rigidly
on a base
and provided with a flap valve at its lower extremity to allow the contents of
the
funnel.to be emptied into an axially aligned cylindrical cup disposed below
the funnel.
The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at
its
respective upper and lower extremities. It is mounted so that the lower
extremity is
140 mm above the upper surface of the base. The cup has an overall height of
90
mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal
volume is 500 ml.
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To carry out a measurement, the Funnel is filled with powder by hand pouring,
the
flap valve is opened and powder allowed to overfill the cup. The filled cup is
removed from the frame and excess powder removed from the cup by passing a
straight edged implement eg; a knife, across its upper edge. The filled cup is
then
weighed and the value obtained for the weight of powder doubled to provide a
bulk
density in g/litre. Replicate measurements are made as required.
The composition is preferably soluble in cold or cool water, i.e. the
composition
readily dissolves/disperses in water at a temperature between about 0oC and
32.2oC,
preferably between about l.6oC and lOoC.
Laundry washine meth
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 components of the invention or
composition
comprising the foaming component of 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.
Abbreviations used in Examples
In the exemplified foaming component and cleaning compositions, the
abbreviated
component identifications have the following meanings:
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS : Sodium C14-C15 linear alkyl sulfate
__ ___
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MES : ~ a-sulpho methylester of C1g fatty acid
CxyEzS : Sodium C 1 x-C 1 y branched alkyl sulfate
condensed
with z moles of ethylene oxide
MBAS~, y : Sodium mid-chain branched alkyl sulfate
having an average of x carbon atoms, whereof
an
average of y carbons comprised in (a) branching
units)
C4g SAS : Sodium C~4-C18 secondary alcohol sulfate
SADExS : Sodium C14-C22 alkyl disulfate of formula
2-(R).C4 H~-
1,4-(S04-)2 where R = C,oOC,s, condensed
with z
moles of ethylene oxide
CxyEz : A Clx-ly branched primary alcohol condensed
with an
average of z moles of ethylene oxide
QAS I : R2.N+(CH3)2(C2H4OH) with R2 = 50%-60%
C9;
40%-50% C 1 i
QAS II : R1.N+(CH3)(C2H40F~2 with R1 = C12'C14
Soap : Sodium linear alkyl carboxylate derived
from an 80/20
mixture of tallow and coconut oils.
TFAA I : C 12-C 14 ~kYl N-methyl glucamide
TFAA II : C 16-C 1 g alkyl N-methyl glucamide
TPKFA : C 12-C 14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
Zeolite A I : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12~ 27H2O having a primary
particle
size in the range from 0.1 to 10 micrometers
Zeolite A II : overdried Zeolite A I
NaSKS-6 : Crystalline layered silicate of formula
8 -Na2Si205
Citric acid I : Anhydrous citric acid
Citric acid II : Citric acid monohydrate
Malic acid : Anhydrous malic acid
Malefic acid : Anhydrous malefic acid
Aspartic acid : Anhydrous aspartic acid
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Carbonate I : Anhydrous sodium carbonate with an average particle
size between 2001tm and 900p.m
Carbonate II : Anhydrous sodium carbonate with an average particle
size between 100p,m and 200~tm
Bicarbonate : Anhydrous sodium bicarbonate with a particle size
distribution between 400~m and 1200~m
Silicate : Amorphous Sodium Silicate (Si02:Na20; 2.0 ratio)
Sodium sulfate : Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4% with
a
particle size distribution between 425p,m and q 850~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000
CMC : Sodium carboxymethyl cellulose
Protease : Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename Savinase
Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO
Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVUIg sold by
NOVO Industries A/S under the tradename Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename Termamyl
60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO
Industries A/S under the tradename Lipolase
Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold
by
NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
PB 1 : Anhydrous sodium perborate bleach of nominal formula
'
NaB02.H202
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Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03.3H2O2
NAC-OBS : (Nonanamido caproyl) oxybenzene sulfonate
in the
form of the sodium salt.
NOBS : Nonanoyl oxybenzene sulfonate in the form
of the
sodium salt
DPDA : Diperoxydodecanedioic acid
PAP : N-phthaloylamidoperoxicaproic acid
NAPAA : Nonanoylamido peroxo-adipic acid
NACA : 6 nonylamino - 6 oxo - capronic acid.
TAED : Tetraacetylethylenediamine
DTPMP : Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under the Trade name bequest
2060
Photoactivated : Sulfonated Zinc or aluminium Phthlocyanine
encapsulated
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-
2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole
QEA : bis {(C2H~0)(C2Ha0)n) (CH3) -N+-C6H12-~-
(CH3)-bis ((C2H50)-(C2H40)n), wherein n=from
20
to 30
SRP 1 : Sulfobenzoyl end capped esters with oxyethylene
oxy
and terephtaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short
block polymer
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Silicone antifoam : Polydimethylsiloxane foam controller with siloxane-
oxyalkytene copolymer as dispersing agent with a ratio
of said foam controller to said dispersing agent of 10:1
to 100:1.
In the following Examples all levels are quoted as parts per weight of the
composition or % by weight of the composition, as indicated:
Particulate Foaming Component Examples
The following examples exemplify particulate foaming components in accord with
the
invention, each of which, or mixtures thereof, can be used in cleaning
compositions.
The particulate components of the invention can be made by any method known in
the art for formation of particles, as described above. The following
particulate
components are formed by formation of a melt of the substantially anhydrous
stabilising agent, and addition of the melt to a premix of the other component
to the
melt, mixing the ingredients thoroughly, whereafter the melt is solidified.
Particles A to J
__~____ ._..._.....__A B ._C .. ..-F.. ...H ...J.....
._........._.-......__._.................. :.............~ E .-
.G....._ - .........._
TFAA U TFAAII- ....-.......31.0D ........_..._...._......_I- _ 10.0
32.0 _........:....__...... ~15.0~~15.0~'~37....._............._.
12.0 25.0
s = -
32.0
C24E3/ C24E5 - - 28.0 - 25.025.0 5.0 15.015.0
-
PEG 4000 5.0 5.3 - 5.0 - - 7.0 5.0 - 5.0
citric acid I 13.5~~~14.0 ~20.0~~15.5~~~ ~16.0~20.0~1~5.0~10.0~~~-~-
~~10.0:
-~~~-~~w~~~~~~~~ ~
.........._...... ..........-._..... ....................._......-
.... .._.......
....... .__... - - - - ...........10.0
Malefic acid - - 10.5
~ - -
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49
sodium carbonate..13 20Ø; ..~.. ......;-~ 150 10.0
I .."'. . 5 .. _.. ...=
E .....
..... ...... ..... ..........i....... ............ ........
...... .. ~~_ .. =-~ ~
~~ w ~ ~~
~
~
sodium carbonate14.0 - 6 14.020.0 10.0 -
II - 0 10.0 5.0
.............................................i..................y..............
.. ..... .......;..............3
......
i i i
i
sodium bicarbonate- - - ' 6.0 - - 10.0 - ~ 5.5 5.0
i i
i = i
Zeolite A II 18.0 20.0 ; - 9.0 10.05.0 14.017.0
~ 3 18.0
5.7
a
'LAS ""'.............................9.0 ...=.....,........12.0"'.. ..i
0.0 i
~. =.. _...... ~.........~..~ 3.0
~. . .
............ ....i............ ........... ......i.............
QAS I/ ~QAS II ...9.0 ..........- - ...6Ø...3.0 _
" _ _ _ _
.............. .................+...... ....._..i............
...........i
TAED/ NOBS! ......... . ~~10.0~~ - ~~ 7.035.0~~
- - - 19.0" - -
NACA-OBS
Perborate! - _ _ _ _ 19.0: 20.0: -
- _
percarbonate
Silicone antifoam- - - - 8.0 - - - i - 5.0
The following examples exemplify cleaning compositions comprising the foaming
component of the invention:
Eaamnle I
The following are high density and bleach-containing detergent formulations
according to the present invention:
a b c
Blown Powder
Zeolite A 5.0 5.0 15.0
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Sodium sulfate 0.0 5.0 0.0
LAS - 5.0 3.0
C45AS 3.0 2.0 4.0
QAS - - 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Particle A 20.0
Particle B - 15.0 -
Particle E - - 10.0
Spray On (on particles)
Encapsulated Perfume 0.3 0.3 0.3
C25E3 - - 2.0
Dry additives
QEA - - 0.5
Citrate 5.0 - 2.0
Bicarbonate - 3.0 -
Carbonate 8.0 10.0 5.0
NAC OB S 6.0 - -
Manganese catalyst - - 0.3
NOBS - 2.0 -
PB 1 14.0 7.0 -
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Citric acid - - 0.5
Protease 1.0 1.0 1.0
Lipase ~ 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
CA 02287000 1999-10-13
WO 98/46715 PCT/IB98/00560 ,
51
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and Miscellaneous)100.0 100.0 100.0
Density (g/litre) 850 850 850
Example 2
The following are high density detergent formulations according to the present
invention:
d a
Particle A 15.0
Particle H 30.0
Spray On
C25E3 - 1.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate - 1.0
NAC OBS 4.1 - _
TAED 0.8 -
Percarbonate 20.0 5.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Amylase 0.6 0.6
CA 02287000 1999-10-13
WO 98/46715 PCT/IB98/00560.
52
QEA 1.0
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
Density {g/litre) 850 850
