Note: Descriptions are shown in the official language in which they were submitted.
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Fabric softening component
Technical Field
The present invention relates to a softening component for use as softener for
fabrics,
comprising a clay and a flocculating agent, a surfactant system and a earner
material. The
component may also be used in detergent compositions.
Background to the Invention
Clays have been used for several years in detergents to provide softening of
the fabrics
washed with the compositions. The have been described as materials which can
be dry-
added to the other detergent granules, or can be mixed with other ingredients.
EP-A-
313146 described clay particles 60% to 99% clay and a humectant, which are
added to a
detergent composition.
Clay flocculating agent have also been known for several years, to improve the
deliver of
the clay to the fabric. EP-A-313146 also describes that the detergents
containing the clay
particles comprise preferably a clay flocculating agent.
The inventors have now found that when the efficiency of the clay deposition
can be
enhanced when the clay and the flocculating agent are present in an intimate
mixture with
one another. Not only does this improve clay deposition efficiency but this
also allows
for the same softness performance to be delivered with reduced levels of clay.
Whilst deposition of the clay is enhanced by the use of the intimate mixtures,
it has been
found that it is also important to effectively distribute the flocculating
clay during the
wash. The inventors have found that this is~ ach.ieved by mixing the mixture
of clay and
flocculating agent with a surfactant. However, the also found that the
delivery is even
further improved when also a powdered or granular carrier material is mixed
with the
clay, flocculating agent and surfactant. Furthermore, the use of the
surfactant improves
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2
the ease of mixing of the clay and the flocculating agent whilst the Garner
material allows
the formation of a non-sticky and easy handable mixture, which can be
processed easily in
to its required form. In this form, the mixture has also be found to more
storage stable,
which is advantages because the mixture can then be stored until final use and
it does not
to be further processed immediately.
It is highly preferred that the carrier material comprises an alkalinity
source and/ or a
builder, because then a mufti-purpose softening component is obtained. Such a
component can be useful in several applications, including as component of a
detergent
composition, as a component of a fabric softener composition, or as washing
and
softening component on its own, in particular for hand washing or washing of
small
washing loads or of washing loads which are not to heavily soiled.
Summary of the invention
The invention relates to a solid fabric softening component comprising
a) a clay;
b) at least 5% of a surfactant system;
c) at least 15% by weight of a solid Garner material;
d) a flocculating agent.
The component is preferably in the form of a spray-dried particle,
agglomerate, or
extrudate. The component may however also be processed a tablet form or bar
form.
The component can be used in any of these forms to treat fabrics, or it can be
used as part
of a detergent compositions or fabric softener composition. The component can
be used
in both automatic washing and hand washing, including also pre-treatment or
soaking, or
post-treatment such as fabric conditioning.
Softenin~component
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The component of the invention comprises at least a clay, a flocculating
agent, a
surfactant and a solid carrier material.
The total level of surfactant in the component is preferably form 5% to 90%,
more
preferably from 10% to 70% or even 60% , more preferably from 15% to 60% or
even
SO% by weight of the component.
Preferably the surfactant comprises at least an anionic sulphate surfactant or
an anionic
sulphonate surfactant. Preferred sulphonate and sulphate surfactants are
described herein
after.
The sulphonate or sulphate surfactant or mixtures thereof are preferably
present at a level
of from 5% to 60% by weight of the component, more preferably from 10% to 60%
or
even from 15% to 50% by weight of the component.
It may be preferred is that the component comprises a nonionic surfactant or
mixtures
thereof, either as only surfactant or combined with other surfactants. The
nonionic
surfactant are preferably present at a level of from 2% to 60% by weight of
the
component, more preferably from 5% to 50% or even from 10% to 45% by weight of
the
component
The Garner material is preferably in granular or powdered form. The Garner
material
comprises preferably an alkalinity source and/ or a builder Preferred
alkalinity sources
are inorganic carbonate salts. Preferred builders (which are often also
alkaline) are
aluminosilicates, crystalline silicates, amorphous silicates, crystalline
layered silicates,
phosphate salts, carboxylic acids or salts thereof. However, also other
inorganic salts
such a sulphate salts can be used.Preferred salts of the types mentioned above
are sodium
salts. It may be preferred that at least one potassium salt is present in the
intimate
mixture with the clay.
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4
The carrier material is preferably present at a level of from 20% to 95% by
weight, more
preferably from 25% to 90% or even to 80% by weight, more preferably even form
30%
to 70% by weight.
Hereby, it can be preferred that the inorganic carbonate salt is present at
least 10% or even
1 S% by of the component, preferably up to levels of 60% or even 50% or even
40% by
weight.
Highly preferred herein is the presence of at least a phosphate salt or
aluminosilicate
builder. Hereby, it can be preferred that the builder, preferably the
phosphate and/ or
alumnisilicate builder is or are present at least 10% or even 15% by of the
component,
preferably up to levels of 60% or even 50% or even 40% by weight.
Whilst silicates are useful and even preferred herein, they are preferably
used in addition
to at least one other builder or alkalinity source.
The clay is preferably present at a level of at least 1 %, more preferably at
a level of from
2% to 60%, more preferably from 5% to 40% or even form 5% to 30% or even from
7%
to 25% by weight of the component.
The component is prepared by mixing the clay, flocculating agent, Garner
material and
surfactant. Thus, the materials are intimately mixed with one another. This
can be done
my any mixing process or granulation process known in the art. However, the
order of
mixing can highly influence the final performance of the component. Preferred
mixing
processes are:
in one embodiment, the clay and flocculating agent are in an intimate mixture
with one
another, obtained by mixing the clay and the flocculating agent, which is
subsequently
dispersed into or with the surfactant system, the carrier material or an
intimate mixture of
the surfactant and the carrier material.
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- in another highly preferred embodiment the flocculating agent and surfactant
system or
part thereof, or the carrier material or part thereof, but preferably both the
surfactant
system and the Garner material or part thereof, are first intimately mixed and
this mixture
is subsequently mixed or dispersed with the clay. Optionally the remaining
Garner
5 material and/ or surfactant is then subsequently mixed with the resulting
mixture.
- in another preferred embodiment the clay is first intimately mixed with the
Garner
material or part thereof, whereafter this mixture is dispersed with or in, or
mixed with the
flocculating agent and the surfactant and optionally the remaining carrier
material.
Optionally, part of the surfactant can be mixed in the first step with the
clay and the
Garner material or part thereof.
The weight ratio of clay to the flocculating polymer is preferably from 1000:1
to 1:1,
more preferably from 500:1 to 1:1, most preferably from 300:1 to 1:1, or even
more
preferably from 80:1 to 10:1, or in certain applications even from 60:1 to
20:1.
The weight ratio of the clay to the Garner material is preferably from 1:30 to
5:1, more
preferably from 1:20 to 3:1, even more preferably from 1:15 to 1:1 or even
from 1:10 to
1:2. The weight ratio of the surfactant to the clay is preferably from 1:30 to
10:1, more
preferably from 1:15 to 5:1, even more preferably from 1:10 to 3:1 or even
from 1:5 to
1:1.
Highly preferred is the presence of a brightener, not only to provide
brighteness or
whiteness of the fabrics, but also to improve the appearance of the component.
The
brightener is preferably present at a level of at least 0.05% by weight, more
preferably at
least 0.1% or even 0.15% or even 0.2% by weight of the component.
The component may also comprise free moisture, preferably not more than 30% by
weight of the component, more preferably from 0.5% to 20% or even from 1% to
15% or
even at least 5% by weight of the component. However, it may be preferred that
water-
sensitive ingredients are present, such as effervescence systems, enzymes,
bleaches,
perfumes, in which case it may be preferred that the free moisture level is
less that the
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levels specified above, e.g. below 12 % by weight, more preferably below 6% or
even
5%, most preferably below 4% or even 3% by weight of the component.
In one preferred embodiment the component comprises an organic or inorganic
acid, in
particular when a carbonate salt is present, to provide effervescence with the
carbonate
salt. Preferred acids include citric acid, tartaric acid, lactic acid, malefic
acid, malic acid,
glutaric acid, adipic acid, acetic acid and aminoacids.
The component may also comprise other fabric care agent such as soil release
polymers,
cellulosic polymer, dye transfer inhibitors, cationic softeners, or mixtures
thereof. Also
present may be perfume components, which is highly preferred , but also
enzymes or
chelating agents.
The component is preferably a spray-dried particle or an agglomerated
particle, or
alternatively an extrudate or flake or it may be processed into the form of a
tablet or bar.
These particle can be made by known granulation, spray-drying, agglomeration,
extrusion
or tabletting methods, involving intimately mixing the ingredients, optionally
adding
water or other solvents and optionally drying.
Clav
The clay herein can be any clay, capable to provide softness to the fabric.
For clarity, it is
noted that the term clay, as used herein, excludes sodium aluminosilicate
zeolite builder
compounds, which however, may be included in the components of the invention
as
Garner material or part thereof.
It may be preferred that the component comprises a mixture of clays.
One preferred clay may be a bentonite clay. Highly preferred are smectite
clays, as for
example are disclosed in the US Patents No.s 3,862,058 3,948,790, 3,954,632
and
4,062,647 and European Patents No.s EP-A-299,575 and EP-A-313,146 all in the
name of
the Procter and Gamble Company.
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7
The term smectite clays herein includes both the clays in which aluminium
oxide is
present in a silicate lattice and the clays in which magnesium oxide is
present in a silicate
lattice. Typical smectite clay compounds include the compounds having the
general
formula A12(Si205)2(OH)2.nH20 and the compounds having the general formula
Mg3(Si205)2(OH)2.nH20. Smectite clays tend to adopt an expandable three layer
structure.
Specific examples of suitable smectite clays include those selected from the
classes of the
montmorillonites, hectorites, volchonskoites, nontronites, saponites and
sauconites,
particularly those having an alkali or alkaline earth metal ion within the
crystal lattice
structure. Sodium or calcium montmorillonite are particularly preferred.
Suitable smectite clays, particularly montmorillonites, are sold by various
suppliers
including English China Clays, Laviosa, Georgia Kaolin and Colin Stewart
Minerals.
Clays for use herein preferably have a largest particle dimension of from 0.01
~m to 800
m, more preferably from lmm to 400 mm, most preferably from Smm to 200 mm.
Particles of the clay mineral compound may be included as components of
agglomerate
particles containing other detergent compounds. Where present as such
components, the
term "largest particle dimension" of the clay mineral compound refers to the
largest
dimension of the clay mineral component as such, and not to the agglomerated
particle as
a whole.
Substitution of small cations, such as protons, sodium ions, potassium ions,
magnesium
ions and calcium ions, and of certain organic molecules including those having
positively
charged functional groups can typically take place within the crystal lattice
structure of
the smectite clays. A clay may be chosen for its ability to preferentially
absorb one canon
type, such ability being assessed by measurements of relative ion exchange
capacity. The
smectite clays suitable herein typically have a cation exchange capacity of at
least 50
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8
meq/100g. U.S. Patent No. 3,954,632 describes a method for measurement of
cation
exchange capacity.
The crystal lattice structure of the clay mineral compounds may have, in a
preferred
execution, a cationic fabric softening agent substituted therein. Such
substituted clays
have been termed 'hydrophobically activated' clays. The cationic fabric
softening agents
are typically present at a weight ratio, cationic fabric softening agent to
clay, of from
1:200 to 1:10, preferably from 1:100 to 1:20. 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.
A preferred commercially available "hydrophobically activated" clay is a
bentonite clay
containing approximately 40% by weight of a dimethyl ditallow quaternary
ammonium
salt sold under the tradename Claytone EM by English China Clays
International.
Organophilic clays may also be used herein. These are are hydrophobically
modified
clays which have organic ions replacing inorganic metal ions by ion exchange
processes
known in the art. These kinds of clay are readily mixable with organic solvent
and have
the capability to absorb organic solvent at the interlayers. Suitable examples
or
organophilic clays useful in the invention are Bentone SD-1, SD-2 and SD-3
from Rheox
of Highstown, N.J.
It may be optional that the clay, and optionally also the flocculating
polymer, is present in
a mixture with a wax and a structuring agent.
Flocculating~ent
The components of the invention may contain a clay flocculating agent,
preferably present
at a level of from 0.005% to 10%, more preferably from 0.05% to 5%, most
preferably
from 0.1 % to 2% by weight of the component.
The clay flocculating agent functions such as to bring together the particles
of clay
compound in the wash solution and hence to aid their deposition onto the
surface of the
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fabrics in the wash. This functional requirement is hence different from that
of clay
dispersant compounds which are commonly added to laundry detergent components
to aid
the removal of clay soils from fabrics and enable their dispersion within the
wash
solution.
Preferred as clay flocculating agents herein are organic polymeric materials
having an
average weight of from 100,000 to 10,000,000, preferably from 150,000 to
5,000,000,
more preferably from 200,000 to 2,000,000.
Suitable organic polymeric materials comprise homopolymers or copolymers
containing
monomeric units selected from alkylene oxide, particularly ethylene oxide,
acrylamide,
acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine.
Homopolymers of, on
particular, ethylene oxide, but also acrylamide and acrylic acid are
preferred.
European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter
and
Gamble Company describe preferred organic polymeric clay flocculating agents
for use
herein.
Inorganic clay flocculating agents are also suitable herein, typical examples
of which
include lime and alum.
Carbonate salts
Suitable alkali and/ or earth alkali inorganic carbonate salts herein include
carbonate and
hydrogen carbonate and percarbonate of potassium, lithium, sodium, and the
like amongst
which sodium and potassium carbonate are preferred. Suitable bicarbonates to
be used
herein include any alkali metal salt of bicarbonate like lithium, sodium,
potassium and the
like, amongst which sodium and potassium bicarbonate are preferred. However,
the
choice of carbonate or bicarbonate or mixtures thereof in the dry effervescent
granules
may be made depending on the pH desired in the aqueous medium wherein the
granules
are dissolved. For example where a relative high pH is desired in the aqueous
medium
(e.g., above pH 9.5) it may be preferred to use carbonate alone or to use a
combination of
carbonate and bicarbonate wherein the level of carbonate is higher than the
level of
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bicarbonate. The inorganic alkali and/ or earth alkali carbonate salt of the
components of
the invention comprises preferably a potassium or more preferably a sodium
salt of
carbonate and/ or bicarbonate. Preferably, the carbonate salt comprises sodium
carbonate,
optionally also a sodium bicarbonate.
5
In one embodiment of the invention, an effervescence source is present,
preferably
comprising an organic acid, such as carboxylic acids or aminoacids, and a
carbonate.
Then it may be preferred that part or all of the carbonate salt herein is
premixed with the
organic acid, and thus present in an separate granular component.
The carbonate may have any particle size. In one embodiment, in particular
when the
carbonate salt is present in a granule and not as separately added compound,
the carbonate
salt has preferably a volume median particle size from 5 to 375 microns,
whereby
preferably at least 60%, preferably at least 70% or even at least 80% or even
at least 90%
by volume, has a particle size of from 1 to 425 microns. More preferably, the
carbon
dioxide source has a volume median particle size of 10 to 250, whereby
preferably at least
60 %, or even at least 70% or even at least 80% or even at least 90% by
volume, has a
particle size of from 1 to 375 microns; or even preferably a volume median
particle size
from 10 to 200 microns, whereby preferably at least 60 %, preferably at least
70% or even
at least 80% or even at least 90% by volume, has a particle size of from 1 to
250 microns.
Builder material
Preferred builders are alumniosilicate materials, such a s zeolites and/ or
phosphate salts.
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. The phosphate builder material most preferably comprises
tetrasodium pyrophosphate or even more preferably anhydrous sodium
tripolyphosphate.
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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.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
Zeolite MAP is described in EP 384070-A. It is defined as an alkali metal
alumino-
silicate of the zeolite P type having a silicon to aluminium ratio not greater
than
1.33, preferably within the range from 0.9 to 1.33 and more preferably within
the
range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not
greater
than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size,
expressed as a ds0 value of from 1.0 to 10.0 micrometres, more preferably from
2.0
to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
The ds0 value indicates that SO% by weight of the particles have a diameter
smaller than
that figure. The particle size may, in particular be determined by
conventional analytical
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techniques such as microscopic determination using a scanning electron
microscope or by
means of a laser granulometer. Other methods of establishing ds0 values are
disclosed in
EP 384070A.
Also preferred may be crystalline layered silicate material, such as SKS-6 (as
sold by
Clariant), and also amorphous silicates, preferably 1.6 or 2 ratio sodium
silicates. The
may be present as powdered material of low density, e.g. below 40gllitre, or
as compacted
materials, e.g. of density of more than 400 g/ litre, for example obtained by
roller
compaction. The may also be present in the form of a mixture with one another,
or with
other builder materials or inorganic salts.
The component may also preferably comprise 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, and mixtures of any of the
foregoing.
The carboxylate or polycarboxylate builder can be momomeric 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 or their acids 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.
The most preferred polycarboxylic acid containing three carboxy groups is
citric acid,
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13
preferably present at a level of from 0.1% to 15%, more preferably from 0.5%
to 8% by
weight of the composition.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed
citrates described in British Patent No. 1,439,000. Preferred polycarboxylates
are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can produce
borate under wash conditions are useful water-soluble builders herein.
Surfactant system
The component comprises a surfactant system. The surfactant system may contain
any
surfactant commonly employed in detergent compositions, such as anionic
surfactants,
nonionic surfactants, cationic surfactants, amphoteric surfactants,
zwitterionic surfactants
or mixtures thereof. As set out above, preferred is that at least an anionic
sulphate and/ or
sulphonate surfactant is present. Also preferred are nonionic surfactants.
When cationic surfactants, zwitterionic surfactants or amphoteric surfactants
are present,
it may be preferred that at least an anionic surfactant or an nonionic
surfactant is present
as well.
Anionic surfactant
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14
Any anionic surfactant useful for detersive purposes is suitable. These can
include salts
(including, for example, sodium, potassium, ammonium, and substituted ammonium
salts
such as mono-, di- and triethanolamine salts) of the anionic sulfate,
sulfonate, carboxylate
and sarcosinate surfactants.
Anionic sulfonates surfactants are preferably present as the anionic
surfactant or part of
the anionic surfactants.
Other suitable anionic surfactants include the isethionates such as the acyl
isethionates, N-
acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
The performance benefits which result when an anionic surfactant is also used
in the
components of the invention are particularly useful for longer carbon chain
length anionic
surfactants such as those having a carbon chain length of C 12 or greater,
particularly of
C14-15 or even up to C16-18 c~bon chain lengths.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use in the components or components
of the
invention include the primary and secondary alkyl sulfates, having a linear or
branched
alkyl or alkenyl moiety having from 9 to 22 carbon atoms or more preferably C
12 to C 1 g
alkyl; alkyl ethoxysulfates; fatty oleoyl glycerol sulfates; alkyl phenol
ethylene oxide
ether sulfates; the CS-C 1 ~ acyl-N-(C 1-Cq, alkyl) and -N-(C 1-C2
hydroxyalkyl) glucamine
sulfates, and sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside
(the nonionic nonsulfated compounds being described herein).
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Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
Cg-C22 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of
ethylene
oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a
C11-C18
most preferably C11-C15 a~Yl sulfate which has been ethoxylated with from 0.5
to 7,
5 preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed
in PCT
Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of a
CS-C20~ more
preferably a C 10-C 16, more preferably a C 11-C 13 (linear) alkylbenzene
sulfonates, alkyl
ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin
sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty
acyl glycerol
sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
The alkyl ester sulfonated surfactant are preferably of the formula
R1 - CH(S03M) - (A)X- C(O) - OR2
wherein R1 is a C6-C22 hydrocarbyl, R2 is a C1-C6 alkyl, A is a C6-C22
alkylene,
alkenylene, x is 0 or l, and M is a cation. The counterion M is preferably
sodium,
potassium or ammonium.
The alkyl ester sulfonated surfactant is preferably a a-sulpho alkyl ester of
the formula
above, whereby thus x is 0. Preferably, R' is an alkyl or alkenyl group of
from 10 to 22,
preferably 16 C atoms and x is preferably 0. RZ is preferably ethyl or more
preferably
methyl.
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It can be preferred that the Rl of the ester is derived from unsaturated fatty
acids, with
preferably 1, 2 or 3 double bonds. It can also be preferred that R' of the
ester is derived
from a natural occurnng fatty acid, preferably palmic acid or stearic acid or
mixtures
thereof.
Dianionic Surfactants
Dianionic surfactants are also suitable anionic surfactants for use in the
components or
components of the present invention. Preferred are the dianionic surfactants
of the
formula:
A-X--M+
R
~B)Z-Y_-M+
where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether,
ester, amine or
amide group of chain length C1 to C2g, preferably C3 to C24, most preferably
Cg to C20,
or hydrogen; A nad B are independently selected from alkylene, alkenylene,
(poly)
alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain
length C 1
to C2g preferably C1 to C5, most preferably C1 or C2, or a covalent bond, and
preferably
A and B in total contain at least 2 atoms; A, B, and R in total contain from 4
to about 31
carbon atoms; X and Y are anionic groups selected from the group comprising
carboxylate, and preferably sulfate and sulfonate, z is 0 or preferably l; and
M is a
cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an
alkali or
alkaline earth metal ion.
The most preferred dianionic surfactant has the formula as above where R is an
alkyl
group of chain length from C 10 to C 1 g, A and B are independently C 1 or C2,
both X and
Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
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Preferred dianionic surfactants herein include:
(a) 3 disulphate compounds, preferably 1,3 C7-C23 (i.e., the total number of
carbons
in the molecule) straight or branched chain alkyl or alkenyl disulphates, more
preferably having the formula:
OSO 3 M +
R
OS03 M+
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C4 to about C 20;
(b) 1,4 disulphate compounds, preferably 1,4 C8-C22 straight or branched chain
alkyl or alkenyl disulphates, more preferably having the formula:
R ~OS03 ' M +
OSO 3 M +
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C4 to about C 1 g; preferred R are selected from octanyl, nonanyl,
decyl, dodecyl,
tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and
(c) 1,5 disulphate compounds, preferably 1,5 C9-C23 straight or branched chain
alkyl or alkenyl disulphates, more preferably having the formula:
OSO 3 M +
R
OS03 M+
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C4 to about C 1 g.
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It can be preferred that the dianionic surfactants are alkoxylated dianionic
surfactants.
A preferred alkoxylated dianionic surfactant has the formula
A-(EO/PO)n X M +
R
B-(EO/PO~ Y M +
where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether,
ester, amine or
amide group of chain length C1 to C2g, preferably C3 to C24, most preferably
Cg to C20,
or hydrogen; A and B are independently selected from, optionally substituted,
alkyl and
alkenyl group of chain length C1 to C2g, preferably C1 to C5, most preferably
C1 or C2,
or a covalent bond; EO/PO are alkoxy moieties selected from ethoxy, propoxy,
and mixed
ethoxy/propoxy groups, wherein n and m are independently within the range of
from
about 0 to about 10, with at least m or n being at least l; A and B in total
contain at least 2
atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y
are anionic
groups selected from the group consisting of sulphate and sulphonate, provided
that at
least one of X or Y is a sulfate group; and M is a cationic moiety, preferably
a substituted
or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.
The most preferred alkoxylated dianionic surfactant has the formula as above
where R is
an alkyl group of chain length from C 10 to C 1 g, A and B are independently C
1 or C2, n
and m are both l, both X and Y are sulfate groups, and M is a potassium,
ammonium, or a
sodium ion.
Mid-chain branched alk~ sulfates or sulphonates
Mid-chain branched alkyl sulfates or sulphonates are also suitable anionic
surfactants for
use in the components or components of the invention. Preferred are the mid-
chain
branched alkyl sulfates.
Preferred mid-chain branched primary alkyl sulfate surfactants are of the
formula
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R R1 R2
I I
CH3CH2(CHZ~,CH(CH2)xCH(CH2)yCH(CH2)ZOS03M
These surfactants have a linear primary alkyl sulfate chain backbone (i.e.,
the longest
linear carbon chain which includes the sulfated carbon atom) which preferably
comprises
from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise
preferably a total of at least 14 and preferably no more than 20, carbon
atoms. In
components or components thereof of the invention comprising more than one of
these
sulfate surfactants, the average total number of carbon atoms for the branched
primary
alkyl moieties is preferably within the range of from greater than 14.5 to
about 17.5.
Thus, the surfactant system preferably comprises at least one branched primary
alkyl
sulfate surfactant compound having a longest linear carbon chain of not less
than 12
carbon atoms or not more than 19 carbon atoms, and the total number of carbon
atoms
including branching must be at least 14, and further the average total number
of carbon
atoms for the branched primary alkyl moiety is within the range of greater
than 14.5 to
about 17.5.
Preferred mono-methyl branched primary alkyl sulfates are selected from the
group
consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-
methyl
pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol
sulfate, 8-
methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl
pentadecanol
sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-
methyl
pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol
sulfate, 5-
methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol
sulfate,
8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl
hexadecanol
sulfate, 11-methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-
methyl
hexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof.
Preferred di-methyl branched primary alkyl sulfates are selected from the
group
consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol
sulfate, 2,5-methyl
tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol
sulfate, 2,8-
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methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyl
tetradecanol
sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyl tetradecanol sulfate,
2,3-methyl
pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol
sulfate,
2,6-methyl pentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methyl
pentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methyl
pentadecanol sulfate,
2,11-methyl pentadecanol sulfate, 2,12-methyl pentadecanol sulfate, 2,13-
methyl
pentadecanol sulfate, and mixtures thereof.
The following branched primary alkyl sulfates comprising 16 carbon atoms and
having
10 one branching unit are examples of preferred branched surfactants useful in
the present
invention components:
5-methylpentadecylsulfate having the formula:
OS03M
CH3
15 6-methylpentadecylsulfate having the formula
CH3
OS03M
7-methylpentadecylsulfate having the formula
OS03M
20 cH3
8-methylpentadecylsulfate having the formula
CH3
OS03M
9-methylpentadecylsulfate having the formula
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OS03M
CH3
10-methylpentadecylsulfate having the formula
CH3
OS03M
wherein M is preferably sodium.
The following branched primary alkyl sulfates comprising 17 carbon atoms and
having two branching units are examples of preferred branched surfactants
according to
the present invention:
2,5-dimethylpentadecylsulfate having the formula:
CH3
OS03M
CH3
2,6-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
2,7-dimethylpentadecylsulfate having the formula
CH3
OS03M
CH3
2,8-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
2,9-dimethylpentadecylsulfate having the formula
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CH3
OS03M
CH3
2,10-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
wherein M is preferably sodium.
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)-R3 wherein R is a C6 to Clg
alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
consisting of
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl
unit connected to a secondary carbon. Preferred secondary soap surfactants for
use herein
are water-soluble members selected from the group consisting of the water-
soluble salts
of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic
acid, 2-
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butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(R1) CH2 COOM, wherein R is a CS-C1~ linear or branched alkyl or alkenyl
group, Rl is
a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and
oleoyl methyl sarcosinates in the form of their sodium salts.
Nonionic surfactant s, s
The detergent component may comprise or also comprise a nonionic surfactant
system
comprising at least two nonionic alkoxylated surfactants.
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and
propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic
condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic
alkoxylated fatty
acid amides, nonionic ethoxylated/propoxylated fatty alcohols, nonionic
ethoxylate/propoxylate condensates with propylene glycol, and the nonionic
ethoxylate
condensation products with propylene oxide/ethylene diamine adducts.
Preferably, at least one of the nonionic surfactants is an alkoxylated alcohol
surfactant as
described herein after.
Also, preferred are nonionic alkoxylated fatty acid amides, which can provide
even more
additional softening to the fabric, or to the skin when the detergent is in
contact with the
skin.
Most preferred is a nonionic surfactant system which comprises at least two
nonionic
alkoxylated alcohol surfactants whereof preferably one surfactant has an
average
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alkoxylation degree of 5 or less and one surfactant has an average
alkoxylation degree of
more than 5. Highly preferred are systems comprising at least a nonionic
alkoxylated
alcohol with an average alkoxylation degree of 3 or S and at least one
nonionic
alkoxylated alcohol having an average alkoxylation degree of from 5.5 to 15,
preferably 6
or 9.
The alkoxylation groups of the nonionic surfactants preferably are propoxylate
groups,
more preferably ethoxylate groups.
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are preferred in
the nonionic
surfactant system herein. The alkyl chain of the aliphatic alcohol can either
be straight or
branched, primary or secondary, and generally contains from 6 to 22 carbon
atoms.
Particularly preferred are the condensation products of alcohols having an
alkyl group
containing from 8 to 20 carbon atoms.
The nonioninc surfactant system of the invention may comprise an alkoxylated
fatty acid
amide, which comprises preferably a compound of the formula
O
Rl C-N (R20)n R3
wherein R, is a C,z-C,g alkyl or alkenyl group, RZ is a CZ-C4 alkylene group,
R3 is a
hydrogen or a C,-C4 alkyl group, R4 is a C,-C4 alkyl group or hydrogen and n
is a number
from 3 to 12.
Preferred alkoxylated fatty acid amides have a R, being a C,Z-C,4 or a C,6 C,g
alkyl group,
RZ being a propylene or more preferably ethylene, n being from 5 to 10, R4
being methyl
or hydrogen, R3 being hydrogen, or a methyl or ethyl group.
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The detergent components herein may also comprise additionally non-alkoxylated
nonionic surfactnats including polyhydroxy fatty acid amides. Those suitable
for use
5 herein have the structural formula R2CONR1Z wherein : R1 is H, C1-C4
hydrocarbyl, 2-
hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof,
preferable C1-C4
alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e.,
methyl); and R2 is a
CS-C31 hydrocarbyl, preferably straight-chain CS-C 19 alkyl or alkenyl, more
preferably
straight-chain Cg-C17 alkyl or alkenyl, most preferably straight-chain C11-C17
alkyl or
10 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.
The detergent components herein may also comprise additionally alkyl-
polysaccharides,
such as are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21,
1986, having
a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide,
e.g., a
polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula:
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to
18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The
glycosyl is
preferably derived from glucose.
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Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the
alkyl amphocarboxylic acids.
S Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
from 0 to 5, preferably from 0 to 3; and each RS is an alkyl or hydroxyalkyl
group
containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3
ethylene
oxide groups. Preferred are C 10-C 1 g alkyl dimethylamine oxide, and 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 incorporated into the detergent
components in accord
with the invention. These surfactants can be broadly described as derivatives
of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary amines,
or derivatives of quaternary ammonium, quaternary 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.
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Cationic Surfactants
Suitable cationic surfactants to be used in the detergent herein include the
quaternary
ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono
C6
C 16, preferably C6-C 10 N-alkyl or alkenyl ammonium surfactants wherein the
remaining
N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Preferred
are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Another suitable group of cationic surfactants which can be used in the
detergent components or components thereof herein are cationic ester
surfactants.
The cationic ester surfactant is a, preferably water dispersible, compound
having
surfactant properties comprising at least one ester (i.e. -COO-) linkage and
at least one
cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have
for example
been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are
separated
from each other in the surfactant molecule by a spacer group consisting of a
chain
comprising at least three atoms (i.e. of three atoms chain length), preferably
from three to
eight atoms, more preferably from three to five atoms, most preferably three
atoms. The
atoms forming the spacer group chain are selected from the group consisting of
carbon,
nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any
nitrogen
or oxygen atom in said chain connects only with carbon atoms in the chain.
Thus spacer
groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages
are
excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-
CH2-
linkages are included. In a preferred aspect the spacer group chain comprises
only carbon
atoms, most preferably the chain is a hydrocarbyl chain.
Cationic mono-alkoxylated amine surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant
preferably of the
general formula I:
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R1 /ApRa
\N+ X
~R3
R (I)
wherein Rl 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 14
carbon atoms; R2 and R3 are each independently alkyl groups containing from
one to
about three carbon atoms, preferably methyl, most preferably both R2 and R3
are methyl
groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X- is an
anion such as
chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical
neutrality; A is
a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0
to about
30, preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group,
having no
greater than 6 carbon atoms whereby the -OH group is separated from the
quaternary
ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred
ApR4
groups are -CH2CH20H, -CH2CH2CH20H, -CH2CH(CH3)OH and
CH(CH3)CH20H, with-CH2CH20H being particularly preferred. Preferred Rl groups
are linear alkyl groups. Linear R1 groups having from 8 to 14 carbon atoms are
preferred.
Another highly preferred cationic mono-alkoxylated amine surfactants for use
herein are
of the formula
R1\ /(C H2C H20 )2-S H
\N+ XO
CH3/ \CH3
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wherein R1 is C 1 p-C 1 g hydrocarbyl and mixtures thereof, especially C 10-C
14 alkyl,
preferably C 10 and C 12 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.
The levels of the cationic mono-alkoxylated amine surfactants used in
detergent
components of the invention is preferably from 0.5% to 30%, more preferably
from 1% to
25%, most preferably from 1 % to 10% by weight of the component.
Cationic bis-alkoxvlated amine surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general
formula II:
Ri ~~R3
R2~ ~A,qR4
(II)
wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18
carbon
atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10
to about 14
carbon atoms; R2 is an alkyl group containing from one to three carbon atoms,
preferably
methyl; R3 and R4 can vary independently and are selected from hydrogen
(preferred),
methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate,
sulfate, or the
like, sufficient to provide electrical neutrality. A and A' can vary
independently and are
each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH20-),
propoxy, butoxy
and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q
is from 1 to
about 30, preferably 1 to about 4, and most preferably both p and q are 1.
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Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
R\ +/CH2CH20H
N X
CH3/ \CH2CH20H
wherein R1 is C 10-C 1 g hydrocarbyl and mixtures thereof, preferably 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) C12-
C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each
monoethoxy.
10 Other cationic bis-alkoxylated amine surfactants useful herein include
compounds of the
formula:
1
R~ ~(CH2CH20~H
N+ X-
R2~ ~(CH2CH20)qH
wherein R1 is C 10-C 1 g hydrocarbyl, preferably C 10-C 14 alkyl,
independently p is 1 to
about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X is
an anion,
1 S 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
20 i-Pr units.
Other ingredients of the component and Compositions containing the com on nent
The component may comprise additional ingredients. These ingredients are
preferably
ingredients commonly employed in laundry detergents or laundry softeners, as
described
25 herein after.
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The fabric softening component of the invention may be present in a detergent
composition or softening compositions. These compositions are preferably
solid, in the
form of granules, extrudates, flakes, bars or tablets.
The compositions can be used in automatic washing or hand washing. Also, the
compositions can be such that they are suitable for pre-treatment or soaking,
or for rinsing
or conditioning of the fabric after the main wash.
The compositions in accord with the invention may also contain additional
detergent
components. The precise nature of these additional components, and levels of
incorporation thereof will depend on the physical form of the composition or
component,
and the precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional
detergent
components selected from additional surfactants, as described above, bleaches,
bleach
catalysts, alkalinity systems, additional builders, additional organic
polymeric
compounds, enzymes, suds suppressers, soaps, lime soap, dispersants, soil
suspension and
anti-redeposition agents soil releasing agents, perfumes, brighteners, photo-
bleaching
agents and additional corrosion inhibitors.
Highly preferred additional ingredients are soil release polymers, in
particular polyesters
or polysaccherides or derivatives thereof, cellulose based polymers, including
carboxy
methyl cellulose, cellulose ethers or ester or amine or amide modified
celluloses,
encapsulated perfumes, effervescence sources, preferably based on carbonate
and acid
compounds, in particular citric acid, malic acid or malefic acid, phosphonate-
builders, dye
transfer inhibitors, and process aids such as hydrotropes. These ingredients
are described
in more detail herein.
Highly preferred may be to include a carboxy methyl cellulose compound at a
level of at
least 0.5% or even 0.75% or even 1% by weight of the composition, or
alternatively, or in
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addition a polysaccheride at a level of at least 0.5% or even 0.75% or even 1%
by weight
of the composition.
It may be preferred that the compositions comprise a cationic softener. Highly
preferred
S water-insoluble quaternary ammonium compounds are those having two C,z-Cza
alkyl or
alkenyl chains, optionally substituted by functional groups such as -OH,-O-,-
CONH,-
COO- etc.
Well known species of substantially water-insoluble quaternary ammonium
compounds
have the formula
R,RZR3R4N X
wherein R, and Rz represent hydrocarbyl groups from about 12 to about 24
carbon atoms;
R3 and R4 represent hydrocarbyl groups containing from 1 to about 4 carbon
atoms; and X
is an anion, preferably selected from halide, methyl sulfate and ethyl sulfate
radicals.
Representative examples of these quaternary softeners include ditallow
dimethylammonium chloride; ditallow dimethyl ammonium methyl sulfate;
dihexadecyl
dimethyl ammonium chloride; di(hydrogenated tallow alkyl)dimethyl ammonium
chloride; dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium
chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated tallow)
dimethyl
ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; di(coconut
alkyl)
dimethyl ammonium chloride. Ditallow dimethyl ammonium chloride,
di(hydrogenated
tallow alkyl) dimethyl ammonium chloride, di(coconut alkyl) dimehtyl ammonium
methosulfate are preferred.
Also suitable herein are the imidaxolinium fabric softening components of US
patent no.
4127489, incorporated by reference. As used herein the term "fabric softening
agent"
excludes, cationic detergent active materials which have a solubility above 10
g/1 in water
at 20°C at a pH of about 6.
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33
Especially preferred is ditallowyl methylamine. This is commercially available
as
Armeen M2HT from AKZO NV, as Genamin SH301 from FARBWERKE HOECHST,
and as Noram M2SH from the CECA COMPANY.
Perhvdrate Bleaches
An preferred additional components of the components or 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 components herein.
1 S Organic Peroxyacid Bleaching-Svstem
A preferred feature of the composition or component is an organic peroxyacid
bleaching
system. In one preferred execution the bleaching system contains a hydrogen
peroxide
source and an organic peroxyacid bleach precursor compound. The production of
the
organic peroxyacid occurs by an in situ reaction of the precursor with a
source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate
bleaches, such as the perborate bleach of the claimed invention. In an
alternative preferred
execution a preformed organic peroxyacid is incorporated directly into the
composition.
Compositions containing mixtures of a hydrogen peroxide source and organic
peroxyacid
precursor in combination with a preformed organic peroxyacid are also
envisaged.
Peroxyacid Bleach Precursor
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
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34
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is
O
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of from
0.5% to 20% by weight, more preferably from 1% to 15% by weight, most
preferably
from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871,
2143231 and
EP-A-0170386.
Leavin~ps
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:
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Y R3 RsY
-O ~ , -O ~ Y , and -O
4
-N-C-R - ~ -N-C-C H-R
R3 , R3 Y ,
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O O
II Y II
-NCH2-CNR4 -N~ /NR4
_O-C-R ~C/ ~C
O ~ O
5
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to
14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4
is H or
10 R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be
substituted by
essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03 M+, -COZ M+, -S04 M+, -N+(R3)4X and
15 O<--N(R3)3 and most preferably -S03 M+ and -COZ M+ wherein R3 is an alkyl
chain
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36
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 Percarboxvlic 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 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
preferably present in the detergent composition, comprising the particle.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide Substituted Alkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ C-NR2C L R~ N-CR2 C-L
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
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37
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.
1 S Preformed organic peroxvacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative
to, an organic peroxyacid bleach precursor compound, a preformed hydrophobic
organic
peroxyacid , typically at a level of from 0.05% to 20% by weight, more
preferably from
1 % to 10% by weight of the composition.
A preferred class of hydrophobic organic peroxyacid compounds are the amide
substituted compounds of the following general formulae:
R~ -C-NR2COOH R~ NCR2 C-OOH
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from about 1 to about 14 carbon
atoms, R2 is
an alkylene, arylene, and alkarylene group containing from about 1 to 14
carbon atoms,
and RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon
atoms. R1
preferably contains from about 6 to 12 carbon atoms. R2 preferably contains
from about
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38
4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted
aryl or
alkylaryl containing branching, substitution, or both and may be sourced from
either
synthetic sources or natural sources including for example, tallow fat.
Analogous
structural variations are permissible for R2. R2 can include alkyl, aryl,
wherein said R2
may also contain halogen, nitrogen, sulphur and other typical substituent
groups or
organic compounds. RS is preferably H or methyl. R1 and RS should not contain
more
than 18 carbon atoms total. Amide substituted bleach activator compounds of
this type are
described in EP-A-0170386. Suitable examples of this class of agents include
(6-
octylamino)-6-oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-
decylamino)-6-
oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, the magnesium
salt of
metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.
4,483,781, U.S.
4,634,551, EP 0,133,354, U.S. 4,412,934 and EP 0,170,386. A preferred
hydrophobic
preformed peroxyacid bleach compound for the purpose of the invention is
monononylamido peroxycarboxylic acid.
Other suitable organic peroxyacids include diperoxyalkanedioc acids having
more than 7
carbon atoms, such as diperoxydodecanedioc acid, diperoxytetradecanedioc acid
and
diperoxyhexadecanedioc acid.
Other suitable organic peroxyacids include diamino peroxyacids, which are
disclosed in WO 95/ 03275, with the following general formula:
II II II
MOCR-(R~ N)n C (NR2)n' -R3-f R2N)m~~ (NR~ )m-RCOOM
wherein:
R is selected from the group consisting of C1-C12 alkylene, CS-C12
cycloalkylene, C6-
C12 arylene and radical combinations thereof;
Rl and R2 are independently selected from the group consisting of H, C1-C16
alkyl and
C6-C12 aryl radicals and a radical that can form a C3-C12 ring together with
R3 and both
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39
nitrogens; R3 is selected from the group consisting of Cl-C12 alkylene, CS-C12
cycloalkylene and C6-C 12 arylene radicals; n and n' each are an integer
chosen such that
the sum thereof is 1; m and m' each are an integer chosen such that the sum
thereof is 1;
and
M is selected from the group consisting of H, alkali metal, alkaline earth
metal,
ammonium, alkanolammonium cations and radicals and combinations thereof.
Other suitable organic peroxyacids are include the amido peroxyacids which are
disclosed
in WO 95/ 16673, with the following general structure:
X-Ar-CO-NY-R(Z)-CO-OOH
in which X represents hydrogen or a compatible substituent, Ar is an aryl
group, R
represents (CH2)n in which n = 2 or 3, and Y and Z each represent
independently a
1 S substituent selected from hydrogen or an alkyl or aryl or alkaryl group or
an aryl group
substituted by a compatible substituent provided that at least one of Y and Z
is not
hydrogen if n = 3. The substituent X on the benzene nucleus is preferably a
hydrogen or a
meta or para substituent, selected from the group comprising halogen,
typically chlorine
atom, or some other non-released non-interfering species such as an alkyl
group,
conveniently up to C6 for example a methyl, ethyl or propyl group.
Alternatively, X can
represent a second amido-percarboxylic acid substituent of formula:-
CO-NY-R(Z)-CO-OOH
in which R, Y, Z and n are as defined above.
MOOC-Rl CO-NR2-R3-NR4-CO-R5 COOOM
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wherein Rlis selected from the group consisting of C1-C12 alkylene, CS-C12
cycloalkylene, C6-C12 arylene and radical combinations thereof; R
Highly preferred herein is phthaloylamido peroxyacid (PAP)
5
Bleach Catalyst
The composition or component can contain a transition metal containing bleach
catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a
transition metal
10 cation of defined bleach catalytic activity, such as copper, iron or
manganese cations, an
auxiliary metal cation having little or no bleach catalytic activity, such as
zinc or
aluminum cations, and a sequestrant having defined stability constants for the
catalytic
and auxiliary metal cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof. Such
15 catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in U.S.
Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include
MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-
20 OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)3, and mixtures thereof. Others are described in
European
patent application publication no. 549,272. Other ligands suitable for use
herein include
1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-
methyl-
25 1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and
mixtures
thereof.
The bleach catalysts useful herein may also be selected as appropriate for the
present
invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612
and U.S. Pat.
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41
5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese
(IV)
complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3-(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a water-soluble
complex of manganese (III), and/or (IV) with a ligand which is a non-
carboxylate
polyhydroxy compound having at least three consecutive C-OH groups. Preferred
ligands
include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol,
meso-erythritol,
meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition metals,
including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands
are of the
formula:
R2 R3
R~ -N=C-B-C=N-R4
wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring.
Said ring can further be substituted. B is a bridging group selected from O,
S. CRSR6,
NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups,
including
substituted or unsubstituted groups. Preferred ligands include pyridine,
pyridazine,
pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally,
said rings may
be substituted with substituents such as alkyl, aryl, alkoxy, halide, and
nitro. Particularly
preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts
include Co, Cu,
Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred
catalysts
include Co(2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt
(II),
trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)202C104, Bis-
(2,2'-
bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II)
perchlorate, and
mixtures thereof.
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42
Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-
dentate
ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2]-
(C104)3.
Other bleach catalysts are described, for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
application, publication no. 224,952, (absorbed manganese on aluminosilicate
catalyst),
U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium
salt),
U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (fernc complex
catalyst),
German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191
(transition metal-containing salts), U.S. 4,430,243 (chelants with manganese
cations and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
The bleach catalyst is typically used in a catalytically effective amount in
the
compositions and processes herein. By "catalytically effective amount" is
meant an
amount which is sufficient, under whatever comparative test conditions are
employed, to
enhance bleaching and removal of the stain or stains of interest from the
target substrate.
The test conditions will vary, depending on the type of washing appliance used
and the
habits of the user. Some users elect to use very hot water; others use warm or
even cold
water in laundering operations. Of course, the catalytic performance of the
bleach
catalyst will be affected by such considerations, and the levels of bleach
catalyst used in
fully-formulated detergent and bleach compositions can be appropriately
adjusted. As a
practical matter, and not by way of limitation, the compositions and processes
herein can
be adjusted to provide on the order of at least one part per ten million of
the active bleach
catalyst species in the aqueous washing liquor, and will preferably provide
from about 1
ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate
this point
further, on the order of 3 micromolar manganese catalyst is effective at
40°C, pH 10
under European conditions using perborate and a bleach precursor. An increase
in
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43
concentration of 3-5 fold may be required under U.S. conditions to achieve the
same
results.
Heave metal ion sequestrant
The compositions or 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 chelation capacity, but preferentially
they show
selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 10%,
preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most
preferably
from 0.3% to 2% 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.
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, l,l
hydroxyethane
diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenediamine
disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine
disuccinic
acid or any salts 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
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44
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.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-
N,N'-
disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof.
Enzvme
Another preferred ingredient useful in the components or compositions herein
is one or
more additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, cellulases, endolases,
esterases,
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 Solway 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.
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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, Duramyl and BAN by Novo
Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/
US
9703635, and in W095/26397 and W096/23873.
Amylase enzyme may be incorporated into the composition in accordance with the
10 invention at a level of from 0.0001 % to 2% active enzyme by weight of the
composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001 % to
2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001
% to 0.5%
by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example,
from a lipase
producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including
Pseudomonas pseudoalcali eg nes or Pseudomas fluorescens. Lipase from
chemically or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is
derived from Pseudomonas nseudoalcaligenes, which is described in Granted
European
Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lams ig nosa and expressing the gene in Aspergillus 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.
Additional organic Pol~nneric Compound
Additional organic polymeric compounds are preferred additional components of
the
compositions or components herein and are preferably present as components of
any
particulate components where they may act such as to bind the particulate
component
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46
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 composition.
Organic polymeric compound is typically incorporated in the detergent
compositions of
the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%,
most
preferably from 0.5% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids or their salts in which the polycarboxylic
acid
comprises at least two carboxyl radicals separated from each other by not more
than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of
such salts are polyacrylates of MWt 1000-5000 and their copolymers with
malefic
anhydride, such copolymers having a molecular weight of from 2000 to 100,000,
especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic acid
such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols,
particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000 and most
preferably about 4000.
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47
Polyethylene oxides are preferred additional ingredients, in particular
present in a particle
with the clay herein, as a humectant, preferably also combined with a wax or
oil.
Highly preferred polymeric components herein are cotton and non-cotton soil
release
polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent
5,415,807,
Gosselink et al., and in particular according to US application no.60/051517.
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:
CH3 CH3
X-(-OCH2CH2)n N+-CH2-CH2--~CH2)a N+-CH2CH20~X
b
(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.
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 S, s
The detergent compositions or the components of the invention, when formulated
for use
in machine washing compositions, may comprise a suds suppressing system
present at a
level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from
0.05%
to 3% by weight of the composition.
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48
Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifoam compounds and 2-
alkyl
alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a detergent
composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component.
Such silicone antifoam compounds also typically contain a silica component.
The term
"silicone" as used herein, and in general throughout the industry, encompasses
a variety of
relatively high molecular weight polymers containing siloxane units and
hydrocarbyl
group of various types. Preferred silicone antifoam compounds are the
siloxanes,
particularly the polydimethylsiloxanes having trimethylsilyl end blocking
units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and
soluble
salts thereof. These materials are described in US Patent 2,954,347, issued
September 27,
1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for
use as
suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably 12
to 18 carbon atoms. Suitable salts include the alkali metal salts such as
sodium,
potassium, and lithium salts, and ammonium and alkanolammonium salts.
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-
alkylinelamines 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.
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A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75% to 95% by weight of the silicone antifoam
compound; and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by
weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from
5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to l:l.l, 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 carrier fluid compound, most preferably comprising a C 16-C 18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to
15, at a level of from S% 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
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chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a
melting point of
from 45°C to 80°C.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane
or
mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and
polycarboxylic
polymers, such as copolymers of laic and acrylic acid.
Also highly preferred is the presence of soap.
10 Polymeric Dve Transfer Inhibiting Agents
The component or 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-
15 oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolyrners or combinations thereof, whereby these polymers
can be
cross-linked polymers.
Optical Brightener
20 Thecomponents but alsothe compositions herein preferably contain from about
0.05% to
5%, more preferably from 0.07 to 3% or even 0.1% to 2.5% by weight of the
component
or from about 0.05% to 5%, more preferably from 0.1 to 3% or even 0.12% to
2.5% by
weight of composition of certain types of hydrophilic optical brighteners.
25 Hydrophilic optical brighteners useful herein include those having the
structural formula:
R1 R2
N H H N
NOON O C C O ljOON
~N H H NO
R2 S03M S03M RI
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wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming canon such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a 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-CBS-X and Tinopal-UNPA-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 canon
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species are
commercially
marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy
Corporation.
Polymeric Soil Release A ent
Polymeric soil release agents, hereinafter "SRA", can optionally be employed
in the
present compositions or components. If utilized, SRA's will generally comprise
from
0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by
weight, of
the compositions.
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Preferred SRA's typically have hydrophilic segments to hydrophilize the
surface of
hydrophobic fibers such as polyester and nylon, and hydrophobic segments to
deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This can
enable stains occurnng subsequent to treatment with the SRA to be more easily
cleaned in
later washing procedures.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by
processes
involving at least one transesterification/oligomerization, often with a metal
catalyst such
as a titanium(IV) alkoxide. Such esters may be made using additional monomers
capable
of being incorporated into the ester structure through one, two, three, four
or more
positions, without, of course, forming a densely crosslinked overall
structure.
Suitable SRA's include a sulfonated product of a substantially linear ester
oligomer
comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy
repeat
units and allyl-derived sulfonated terminal moieties covalently attached to
the backbone,
for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel
and E.P.
Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl
alcohol; (b)
reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-
propylene glycol
("PG") in a two-stage transesterification/oligomerization procedure; and (c)
reacting the
product of (b) with sodium metabisulfite in water. Other SRA's include the
nonionic end-
capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
4,711,730,
December 8, 1987 to Gosselink et al., for example those produced by
transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT,
PG and
poly(ethyleneglycol) ("PEG"). Other examples of SR.A's include: the partly-
and fully-
anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to
Gosselink,
such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric
compounds of
U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT,
methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or
PG,
Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially
sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31,
1989 to
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53
Maldonado, Gosselink et al., the latter being typical of SRA's useful in both
laundry and
fabric conditioning products, an example being an ester composition made from
m-
sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably
further
comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene
terephthalate with polyethylene oxide or polypropylene oxide terephthalate,
see U.S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975;
cellulosic
derivatives such as the hydroxyether cellulosic polymers available as METHOCEL
from
Dow; the Cl-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
4,000,093,
December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an
average
degree of substitution (methyl) per anhydroglucose unit from about 1.6 to
about 2.3 and a
solution viscosity of from about 80 to about 120 centipoise measured at
20°C as a 2%
aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE
SM200, which are the trade names of methyl cellulose ethers manufactured by
Shin-etsu
Kagaku Kogyo KK. Also highly preferred are polysaccheride polymers.
Additional classes of SRA's include: (I) nonionic terephthalates using
diisocyanate
coupling agents to link polymeric ester structures, see U.S. 4,201,824,
Violland et al. and
U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups
made by
adding trimellitic anhydride to known SRA's to convert terminal hydroxyl
groups to
trimellitate esters. With the proper selection of catalyst, the trimellitic
anhydride forms
linkages to the terminals of the polymer through an ester of the isolated
carboxylic acid of
trimellitic anhydride rather than by opening of the anhydride linkage. Either
nonionic or
anionic SRA's may be used as starting materials as long as they have hydroxyl
terminal
groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes
include:
(III) anionic terephthalate-based SRA's of the urethane-linked variety, see
U.S. 4,201,824,
Violland et al.;
Other Optional Ingredients
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Other optional ingredients suitable for inclusion in the compositions or
components of the
invention include perfumes, colours and other filler salts as replacement for
sulphate filler
salt.
Also, preferably combined with a carbonate salt, minor amounts (e.g., less
than about
20% by weight) of neutralizing agents, buffering agents, phase regulants,
hydrotropes,
enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-
oxidants,
bactericides, photo-bleaches, speckles, dyes, such as those described in US
Patent
4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by
reference), can
be present.
Form of the Compositions
The composition of the invention can be made via a variety of methods,
including dry-
mixing, agglomerating, compaction, or spray-drying of the various compounds
comprised
in the detergent component, or mixtures of these techniques.
The compositions herein can take a variety of physical forms including liquid,
but
preferably solid forms such as tablet, flake, pastille and bar, and preferably
granular
forms.
The compositions in accord with the present invention can also be used in or
in
combination with bleach additive compositions, for example comprising chlorine
bleach.
Detergent compositions herein, in particular laundry detergents, preferably
have a bulk
density of from 280 g/litre to 200 g/litre, or preferably from 300 g/litre or
even 350g/litre
or 420g/litre to 2000g/litre or more preferably to 1500g/litre or 100 g/litre
or even to
700g/litre.
Chlorine-Based Bleach
The detergent compositions can include as an additional component a chlorine-
based
bleach. However, since preferred detergent compositions of the invention are
solid, most
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liquid chlorine-based bleaching will not be suitable for these detergent
compositions and
only granular or powder chlorine-based bleaches will be suitable.
Alternatively, the detergent compositions can be formulated such that they are
chlorine-
5 based bleach-compatible, thus ensuring that a chlorine based bleach can be
added to the
detergent composition by the user at the beginning or during the washing
process.
The chlorine-based bleachis such that a hypochlorite species is formed in
aqueous
solution. The hypochlorite ion is chemically represented by the formula OCI-.
Those bleaching agents which yield a hypochlorite species in aqueous solution
include
alkali metal and alkaline earth metal hypochlorites, hypochlorite addition
products,
chloramines, chlorimines, chloramides, and chlorimides. Specific examples of
compounds of this type include sodium hypochlorite, potassium hypochlorite,
monobasic
1 S calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated
trisodium phosphate
dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate
sodium
dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-
dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine
B
and Dichloramine B. A preferred bleaching agent for use in the compositions of
the
instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture
thereof.. A
preferred chlorine-based bleach can be Triclosan (trade name).
Most of the above-described hypochlorite-yielding bleaching agents are
available in solid
or concentrated form and are dissolved in water during preparation of the
compositions
of the instant invention. Some of the above materials are available as aqueous
solutions.
Laundrv Washing Method
Machine laundry methods herein typically comprise treating soiled laundry with
an
aqueous wash solution in a washing machine having dissolved or dispensed
therein an
effective amount of a machine laundry detergent composition in accord with the
invention. By an effective amount of the detergent composition it is meant
from l Og to
300g of product dissolved or dispersed in a wash solution of volume from 5 to
65 litres,
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as are typical product dosages and wash solution volumes commonly employed in
conventional machine laundry methods.
The compositions herein can be useful in both conventional washing machines
and low-
s water fill washing machines.
In a preferred use aspect the composition hand washing. In another preferred
aspect the
detergent composition is a pre-treatment or soaking composition, to be used to
pre-treat or
soak soiled and stained fabrics.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
LAS : Sodium linear 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 Clx-Cly alkyl sulfate condensed with z moles of
ethylene oxide
CxyEz : C 1 x-C 1 y predominantly linear primary alcohol condensed
with an average of z moles of ethylene oxide
QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14
QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = Cg - C11
SADS : Sodium C,4 Cz2 alkyl disulfate of formula 2-(R).C4 H,.-1,4
(S04-)Z where R = C,~C,B
SADE2S : Sodium C,4-C22 alkyl disulfate of formula 2-(R).C4 H,.-1,4-
(S04-)Z where R = C,o C,B, condensed with z moles of
ethylene oxide
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MES : x-sulpho methylester of C, 8 fatty acid
APA : Cg - 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 1 g alkyl N-methyl glucamide
TPKFA : C 16_C 1 g topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
10TSPP : Tetrasodium pyrophosphate
Zeolite A . Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12~27H20 having a primary particle
size
in the range from 0.1 to 10 micrometers (weight
expressed
on an anhydrous basis)
15NaSKS-6 : Crystalline layered silicate of formula 8-
Na2Si205
Citric acid : Anhydrous citric acid
Borate : Sodium borate
Carbonate : Anydrous sodium carbonate with a particle
size between
200~m and 900~m
20Bicarbonate : Anhydrous sodium bicarbonate with a particle
size
distribution between 400~m and 1200um
Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1)
Sulfate . Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
25Citrate : Tri-sodium citrate dihydrate of activity
86.4% with a
particle size distribution between 425~m and
850um
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular
weight about 70,000
MA/AA (1) : Copolymer of 4:6 maleic/acrylic acid, average
molecular
30 weight about 10,000
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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
Amylase II : Amylolytic enzyme, as disclosed in PCT/ US9703635
Lipase : Lipolytic enzyme, having 2.0% by weight of
active
enzyme, sold by NOVO Industries A/S under
the
tradename Lipolase
Lipase II : 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 : Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
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PB 1 : Anhydrous sodium perborate bleach of nominal formula
NaB02.H202
Percarbonate : Sodium percarbonate of nominal formula
2Na2C03.3H202
DOBS : Decanoyl oxybenzene sulfonate in the form of the sodium
salt
DPDA : Diperoxydodecanedioc acid
NOBS . Nonanoyloxybenzene sulfonate in the form of the sodium
salt
NACA-OBS : (6-nonamidocaproyl) oxybenzene sulfonate
LOBS : Dodecanoyloxybenzene sulfonate in the form of the
sodium salt
DOBS : Decanoyloxybenzene sulfonate in the form of the
sodium salt
DOBA : Decanoyl oxybenzoic acid
TAED : Tetraacetylethylenediamine
DTPA : Diethylene triamine pentaacetic acid
DTPMP . Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under the Tradename bequest
2060
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S)
isomer in the
form of its sodium salt.
Photoactivated : Sulfonated zinc phthlocyanine encapsulated
in bleach (1)
dextrin soluble polymer
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
HEDP : 1,1-hydroxyethane diphosphonic acid
PEGx : Polyethylene glycol, with a molecular weight
of x
(typically 4,000)
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PEO : Polyethylene oxide, with an average molecular
weight of
50,000
TEPAE . Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidasole, with an average molecular
weight of
5 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
10 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)-(C2H40))n, wherein n = from
20 to 30
PEI . Polyethyleneimine with an average molecular
weight of
15 1800 and an average ethoxylation degree
of 7 ethyleneoxy
residues per nitrogen
Clay I : Bentonite clay
Clay II : Smectite clay
Flocculating agent polyethylene oxide of average molecular
I : weight of
20 between 200,000 and 400,000
Flocculating agent polyethylene oxide of average molecular
II : weight of
between 400,000 and 1,000,000
Flocculating agent polymer of acrylamide and/ or acrylic acid
III : of average
molecular weight of 200,000 and 400,000
25 SRP I : Anionically end-capped polyester soil release
polymer
SRP II : Polysaccheride soil release polymer
SRP 1 : Nonionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short
block polymer
30 Silicone antifoam Polydimethylsiloxane foam controller with
: siloxane-
oxyalkylene copolymer as dispersing agent
with a ratio of
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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
Wax : Paraffin wax
Speckle : Coloured carbonate salt or organic carboxylic acid /
salt
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The following are components in accord with the invention (in weight % by
weight of
component):
Component I II III IV V VI VII VIII IX X XI XII
Clay I and/10. 15. 8.0 7.0 5.0 10.20.0 25.0 8.0 10. 10. 15.0
or 0 0 0 0 0
II
Flocculating0.1 0.5 1.0 2.0 2.5 1.03.0 0.2 0.1 1.0 0.5 2.0
agent I
or II
LAS 10. 8.0 18. 20. - - - - 30. 35. - 18.0
0 0 0 0 0
TAS 2.0 - - - 3.0 6.0- - - - - -
C24AS 2.0 - 4.0 - 10. 20 - - - - - -
0
MBAS - - - - 5.0 - - - - - 12. -
0
C24E7 or - - - - 2.0 - 6.0 - - 2.0 - -
E9
C24E3 or - - - - 2.0 6.0 - - - 2.0
E4
QAS 1.0 - - - - - - 2.0 - 4.0 - -
malic acid - 2.0 - 2.0 - - 2.0 - 5.0 - -
citric acid- - 4.0 - - - - 5.0 - - -
carbonate 10. 15. 10. 12. 4.0 - 20.0 10.0 5.0 S.0 5.0 -
0 0 0 0
bicarbonate- - - - 6.0 - - - - - - -
zeolite 15. - - - 20. - - - - 20. 15. 5.0
A or 0 0 0 0
MAP
STPP - 10. 15. 30 - 18.15.0 20.0 30. - - 5.0
0 0 0 0
silicate 5.0 10 5.0 7.0 - - 4.0 2.0 - 5.0 -
SKS-6 2.0 - - - - - 5.0 - - 5.0 - -
MA/AA 1.0 - - - - - - - - 1.0 1.0 -
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sulphate - - - - - 5.0 - - - - 5.0 -
brightener 0.1 0.10.0 0.2 0.5 0.3 - 0.1 - 0.8 1.0 -
5
SRP _ _ _ _ _ 1.5 - _ - 0.8 - _
TAED - - 5.0 - - - - - - - -
Desiccant# - - 2.0 - 2.0 - - - - - - -
HEDP/ - - - - 0.5 - - 2.0 1.0- - 0.8
EDDS
STS 0.5 0.7- - - 1.0 2.0 - - - 2.0 -
CMC - - - - - 1.2 - - - - 1.0 0.5
percarbonate- - 7.0 - - 3.0 - - - - 10. -
0
sudsuppresso0.5 0.5- - 0.5 1.0 0.8 0.5 - - 2.0 -
r/ soap
enzyme 1.0 - - - - - - 1.0 2.0- - -
moisture
perfume - - 1.0 2.0 0.5 - - - 0.82.0 - -
PEG 4000 - 1.0- - - 1.0 - - - - - -
# (overdried or anhydrous salts/ zeolite or overdried zeolite or silica
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In the following examples all levels are quoted as % by weight of the
composition:
Example 1
The following detergent formulations in the form of a tablet, bar or granular
formulation
are in accord with the invention.
A B C D
Component I- XII balance balance balance bablance
Spray on
Brightener 0.02 - - 0.02
C45E7 or E9 - - 2.0 1.0
C45E3 or E4 - - 2.0 4.0
Perfume 0.5 - 0.5 0.2
Silicone antifoam 0.3 - - -
Dry additives
QEA - - - 1.0
HEDP/ EDDS 0.3 - 0.5 0.5
Sulfate 2.0 - 0.5 1.0
Carbonate 2.0 10. 15.0 12.0
Citric acid 2.5 - - 2.0
QAS - - 0.5 0.5
SKS-6 3.5 - - 5.0
Percarbonate - - 15.0 9.0
PB4 - - - 3.0
TAED/ NOB S - - - 5.0
PAP - - 2.0 -
Protease 1.0 1.0 1.0 1.0
Lipase - 0.4 - 0.2
Amylase 0.2 0.2 0.2 0.4
Brightener 0.05 - - 0.05
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Perfume 1.0 0.2 0.5 0.3
Speckle 1.2 0.5 2.0 -
Misc/minor to 100%
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Example 2
The following detergent formulations in the form of a tablet, bar or granular
formulation
are in accord with the invention.
E F G H I J
Component I-XIIbalancebalancebalance balancebalance balance
Spray on
C45E7 - 2.0 - - 2.0 2.0
C25E9 3.0 - - - - -
C23E9 - - 1.5 2.0 - 2.0
Perfume 0.3 0.3 0.3 2.0 0.3 0.3
Agglomerates
C45AS 5.0 5.0 - 2.0 5.0 -
LAS 2.0 2.0 7.0 - - 8.0
STPP/ Zeolite 7.5 7.5 7.5 8.0 7.5 7.5
A
Carbonate 4.0 4.0 4.0 5.0 4.0 4.0
PEG 4000 0.5 0.5 0.5 - 0.5 0.5
Misc (water 2.0 2.0 2.0 2.0 2.0 2.0
etc)
Dry additives
Citric acid - - - - 2.0 -
PB4 - 3.0 - - - -
PB 1 - - 4.0 1.0 - -
Percarbonate 12.0 - - 1.0 - 2.0
Carbonate - 5.3 20.0 5.0 14.0 24.0
NOBS 0.5 - 0.4 0.3 - 0.6
PAP - 0.9 - - 0.3
TAED 0.6 0.4 0.6 0.3 0.9 0.5
Methyl cellulose0.2 - - - - 0.5
DTPA 0.7 0.5 1.0 0.5 0.5 1.2
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Speckle 0.3 0.2 2.0 - 0.7 0.5
SKS-6 8.0 - - - - -
STS - ~ - 2.0 - 1.0 -
Cumene sulfonic- 1.0 - - - 2.0
acid
Lipase 0.2 - 0.2 - 0.2 0.4
Cellulase 0.2 0.2 0.2 0.3 0.2 0.2
Amylase II 0.2 - 0.1 - 0.2 -
Protease 0.5 0.5 0.5 0.3 0.5 0.5
PVPVI - - - - 0.5 0.1
PVP - _ _ _ 0.5 _
PVNO - - 0.5 0.3 - -
QEA - - - - 1.0 -
SRP I, II, or 0.2 0.5 0.3 - 0.2 -
III
Silicone antifoam0.2 0.4 0.2 - 0.1 -
Mg sulfate - - 0.2 - 0.2 -
Misc/minors
to
100%
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Example 3
The following detergent formulations in the form of a tablet, bar or granular
formulation
are in accord with the invention.
K L M N
Component I-XII balance balance balance balance
Spray on
C25E3 or E4 - - - 2.0
C45E5 or E7 - - - 2.0
Brightener/ photobbleach- - 0.5 0.5
Perfume 0.2 0.3 0.3 -
Dry additives
Carbonate S.0 10.0 13.0 S.0
PVPVI/PVNO 0.5 - 0.3 -
Protease 1.0 1.0 1.0 0.5
Lipase 0.4 - - 0.4
Amylase 0.1 - - 0.1
Cellulase 0.1 - - 0.1
DTPA 0.5 0.3 0.5 1.0
PB1 5 3.0 10 4.0
PAP / DOBA 1.0 - 0.4 -
TAED 0.5 0.3 0.5 0.6
Sulfate 4.0 5.0 - 5.0
SRP I, II or III 0.2 0.4 1.0 0.5
Sud supressor - 0.5 - -
Speckle 1.8 0.8 0.7 -
Flocculating agent - - 0.1 0.2
Perfume (starch) - 0.2 0.3 0.5
Misclminor to 100%
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Example 6
The following detergent formulations in the form of a tablet, bar or granular
formulation
are in accord with the invention.
O P Q R S
Component I balancebalance balance balance balance
-XII
Agglomerate
Clay 9.0 - -
Wax 0.5 - -
Glycerol 0.5 - -
Agglomerate
LAS 15.0 5.0 5.0
TAS 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 - - 0.3 0.3
C45E7 or E9 - - 2.0 2.0
C25E3 or E4 2.0 - - 2.0
Dry additives
Citrate or 2.5 - 2.0 2.5 2.5
citric
acid
Clay I or II - 3.0 3.0 - -
Flocculating - - - - -
agent
I or II
Bicarbonate - 3.0 - - -
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Carbonate 15.0 - - 5.0 11.0
TAED 1.0 2.0 5.0 1.0 -
Sodium perborate6.0 7.0 10.0 6.0 -
or percarbonate
SRPI,IIorIII 0.2 0.1 0.2 0.5 0.3
CMC or nonionic1.0 1.5 0.5 - -
cellulose ether
Protease 0.3 1.0 1.0 0.3 0.3
Lipase - 0.4 0.4 - -
Amylase 0.2 0.6 0.6 0.2 0.2
Cellulase 0.2 0.6 0.6 0.2 0.2
Silicone antifoam- 5.0 5.0 - -
Perfume (starch)0.2 0.3 - - -
Speckle 0.5 0.5 0.1 - 1.0
SKS-6 (silicate3.5 - - - 3.5
2R)
Photobleach 0.1 - - 0.1 0.1
Soap 0.5 2.5 - 0.5 0.5
Sodium sulfate- 3.0 - - -
Misc/minors 100.0 100.0 100.0 100.0 100.0
to
100%
Density (g/litre)850 850 850 850 850
