Note: Descriptions are shown in the official language in which they were submitted.
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SOLID DETERGENT COMPOSITIONS
Technical Field of the Invention
The invention relates to solid detergent compositions comprising
aluminosilicate builder
and surfactants comprised in two or more components which have an improved
cleaning
performance. an improved delivery to the wash and a reduced residue formation
on the
fabrics.
Background to the Invention
All detergents on the market contain surfactants and builders. One of the most
commonly
used builders in phosphate-free detergents are aluminosilicates. They are
inexpensive
builders, which have as an additional benefit that they are easy to process.
They are in fact
useful process aids because they are very good structurants, binders or
carrier materials
for other detergent ingredients. Therefore, most detergents comprise a base
powder, made
by spray-drying a slurry of aluminosilicate and surfactant or by agglomerating
aluminosilicate and surfactant. Furthermore, aluminosilicates are useful as
dusting agent,
to reduce the stickiness or caking of the product.
A problem encountered with these detergents comprising a builder system
containing
aluminosilicates, it that they tend to cause fabric residues. These residues
contain
detergent products which is entrapped in the fabrics and/ or are insoluble in
water. They
are noticeable by the consumer as spotting on the fabric.
Another problem encountered with, in particular solid, detergents is their
tendency to gel
upon contact with water. This leads to poor dispensing of the product from the
dispensing
drawer or from a dispensing device, and also to poor dissolution of the
product into the
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wash water. This results in residues in the drawer, dispensing device, washing
machine
and on the fabrics, which may be noticeable as spots on the fabric. It has
been found that
in particular surfactants gel upon contact with water.
The inventors have now surprisingly found that this problems in particular
arises when
the surfactants and the aluminosilicates in the detergent are in close contact
with one
another, for example when they are in the detergent in an intimately mixture.
This is for
example the case in most known and used base powders, which are agglomerates
or
spray-dried powders containing. The inventors have now found that the residue
formation problem but also the gelling problem or dissolution or dispensing
problem
mainly arises in most known products, when about all the anionic surfactants
and
aluminosilicates are intimately mixed with one another. When the degree of
intimate
mixing is reduced or even avoided completely, they have found that these
problems are
reduced or even solved completely.
Thus, the inventors have found a solution which still allows the incorporation
of
aluminosilicates and surfactants in detergent, but in a different manner: the
invention
provides thereto detergents comprising at least two components comprising the
surfactants and the aluminosilicate in such a manner that a limited degree of
intimate
mixing occurs.
The detergents of the invention have a reduced fabric residue, in particular
of insoluble
detergent ingredients, gelling, an improved dispensing and dissolution. It has
been found
that these benefits are obtained by any convention way of introducing
detergent to the
wash, including by use of a dispensing drawer, a dispensing device or by
addition of the
detergent in the washing prior to addition of the wash load or addition of the
detergent on
top of the wash load.
The compositions may comprise an effervescence system to further aid the
dispensing or
dissolution or foaming.
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3
Summary of the Invention
The invention provides a detergent composition comprising an aluminosilicate
builder
and an anionic surfactant and comprising (n) components (i), n being at least
2, whereby
the level of aluminosilicate builder in said components together is at least
5% by weight
of the composition and the level of the anionic surfactant in said components
together is
at least 5% by weight of the composition, and whereby the degree of mixture
(M) of the
anionic surfactant and the aluminosilicate builder is from 0 to 0.7, M being
~ni=1 '1al
a is the fraction of the anionic surfactant,of the composition comprised in
component (i);
~ is the fraction of the aluminosilicate of the composition comprised in
component (i) and
~5 wherein said aluminosilicate builder is in crystalline form and wherein
said
composition is phosphate-free, free of amorphous silicate, and substantially
free of spray-on
nonionic alkoxylated alcohol surfactants and further wherein at least one
component is made
by a spray-drying process and at least one component is made by an
agglomeration process
and wherein said component is a mixture of ingredients and each component
represents a
discrete part of the overall detergent composition.
The composition is in particular in granular form, in the form of an
extrudate, marumerate
or pastille, or in the form of an tablet.
The invention also relates to the use in a detergent composition of at least
two
components which comprise together an aluminosilicate at a level of at least
5% by
weight of the composition and an anionic surfactant at a level of at least 5%
by weight of
the composition or mixtures thereof, whereby the degree of mixture (M) of the
anionic
surfactant and the aluminosilicate builder is from 0 to 0.7 for improvement of
the delivery
of the detergent to the washing water, M being as defined above.
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3a
The detergent compositions have an improved delivery to the washing water.
This means
for the purpose of the invention that the compositions provide a reduction of
fabric
residues, in particular of water-insoluble detergent ingredients such as the
aluminosilicate,
an improvement of the dispensing of the detergent composition, an improvement
in the
dissolution of the detergent, a reduction in gelling of the detergent and / or
a reduction of
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lump formation of the detergent on the fabrics and for bleach-containing
compositions, an
reduced risk of fabric damage.
Detailed Description of the Invention
The detergent composition herein comprise at least two components which
comprise an
anionic surfactant or an aluminosilicate or mixtures thereof, whereby if
mixtures of
aluminosilicate and the surfactant are present in one or more of the
components, the
degree of mixture M is less than 0.7, as defined by the formula. Thus, each
component
comprises part or all of the aluminosilicate, all or part of the anionic
surfactant or
mixtures thereof, provided that M is from 0 to 0.7.
The components of the detergent composition of the invention comprise each at
least two
ingredients, including the anionic surfactant and/ or the aluminosilicate,
which are
intimately mixed. This means for the purpose of the invention that the two or
more
ingredients the component are substantially homogeneously divided in the
component.
Preferably, a component is such that when it comprises an anionic surfactant,
the level of
the anionic surfactant is less than 95%, preferably less than 85% or even less
than 80% by
weight of the component, whereby it may be preferred that the level of the
anionic
surfactant is at least 5%, preferably at least 10% more preferably at least
20% or even at
least 30% or even 35% by weight of the component.
Preferably, a component is such that when it comprises an aluminosilicate, the
level of the
aluminosilicate is less than 95%, preferably less than 85% or even less than
80% by
weight of the component, whereby it may be preferred that the level of the
aluminosilicate
is at least 5%, preferably at least 10% by weight of the component.
It should be understood that the detergent composition herein may also
comprise
additional intimately mixtures which are free of anionic surfactant and free
of
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aluminosilicate. Also, the detergent composition may comprise additional
ingredients
which are not in an intimate mixture with another ingredient and thus not
comprised in a
component of the composition, as defined herein. For example, the composition
may
comprise a detergent ingredient sprayed onto the components herein or dry-
added to the
5 components herein.
The components together comprise the aluminosilicate builder at a level of
least 5% by
weight of the composition of and the anionic surfactant at a level of at least
5% by weight
of the composition. Preferably, the components comprise the aluminosilicate at
a level of
at least 7%, or more preferably at least 10% or even 15% by weight of the
composition.
Depending on the precise formulation of the composition and the conditions of
use, the
compositions of the invention can even comprise higher levels of
aluminosilicate, such as
more than 20% or even more than 25%, whilst still providing an improved
delivery of the
detergent to the wash.
Preferably at least 7% or more preferably at least 10% or even at least 12% by
weight of
the composition of anionic surfactant is present in the components. Depending
on the
precise formulation of the composition and the conditions of use, it may be
preferred to
have levels of anionic surfactants of 18% by weight of the composition or
more.
It may be preferred that the detergent composition comprises additional dry-
added
aluminosilicate, in particular to dust the detergent components to reduce the
risk of
caking and/ or to provide whiteness to the product.
Preferably, M is less than 0.65, or even less than 0.45 or even 0.4 or even
0.35. It may be
preferred that M is 0, and that thus no components are present in the
detergent
composition which comprise both aluminosilicate and anionic surfactants.
Whether this is
preferred will for example depend the levels of aluminosilicate and anionic
surfactant in
the detergent, on the other ingredients present in the formulation and the
amount of
components present in the formulation.
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The components herein preferably are particles, having a particle size of at
least 50
microns, preferably the particles have an weight average particle size of more
than 150 or
more than 250 microns or even more than 350 microns, as measured by sieving
the
composition on sieves of different mesh size, and calculating the fraction
which remain
on the sieve and the fraction which passes through the sieve.
It may be preferred that at least one component is made by a spray-drying
process, as
known in the art, and at least one component is made by an agglomeration
process, as
known in the art.
Preferably, the density of the components is from 250 g/litre to 1500 g/litre,
more
preferably at least one of the components, preferably all of the components,
has a density
from 400 g/litre to 1200gr/litre, more preferably from 500 g/litre to
900g/litre.
A highly preferred additional ingredient of the detergent compositions herein
may be
oxygen based bleach, preferably containing an hydrogen peroxide source,
preferably a
perhydrogen compound and a bleach activator, described herein after. It has
been found
that the improved product delivery to the wash results in an improved delivery
of the
bleach system therein, which reduces the risk of deposition of bleach on the
fabric and the
risk of patchy fabric damage.
Another preferred additional ingredient is one or more additional builder
materials, such
as one or more monomeric, oligomeric or polymeric carboxylate builders and/ or
crystalline layered silicate builder material, described herein after.
Also, depending on the use of the composition and the specific formulation,
the detergent
composition may be substantially free of specific spray-on nonionic
alkoxylated alcohol
surfactants, which have been found to cause gelling or dispensing or
dissolution
problems. It may then be preferred that the composition comprises other
nonionic
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surfactants, preferably nonionic surfactants which are solid at room
temperature. A
further advantage can be that the omission of sprayed-on nonionic alkoxylated
alcohols
allows the reduction or omission of powdered materials normally required to
dust the
detergent particles containing these liquid nonionic surfactants, such as fine
aluminosilicates. This not only reduces the process complexity, but moreover
reduces the
degree of mixing or contact of the s and surfactants.
Furthermore, the inventors have found that in certain embodiments of the
invention it
may be beneficial to reduce the degree of mixing between the aluminosilicate
and one or
more of the organic polymeric compounds, when present, for example
flocculation
polymers and polycarboxylate polymers, as described herein. The degree of
mixture of
the aluminosilicate and one or more of these polymers can be determined by the
formula
above, wherein a would indicate the weight fraction of the specific polymer in
a certain
component. It has been found that this may reduce the fabric residue formation
on the
fabrics, in particular of water-insoluble components, such as the
aluminosilicate.
It may also be useful that in certain embodiments of the invention , the
degree of mixing
between amorphous silicate and an anionic surfactant is reduced, when an
amorphous
silicate is present, in particular in mixtures containing anionic surfactant
which are to be
spray-dried, it may be beneficial to reduce the amount of silicate present,
for example to
levels of less than 3% by weight of the mixture, or even less than 2%, or even
less thanl%
or even 0% by weight of the mixture.
Alurninosilicate
Suitable aluminosilicates herein are zeolites which 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 aluminosilicates are in preferably in hydrated form and are
preferably
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crystalline, containing from 10% to 28%, more. preferably from 18% to 22%
water in
bound form. However, it may be useful to incorporate overdried
aluminosilictaes.
The aluminosilicatescan 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.
Anionic Surfactant
Any anionic surfactant can be incorporated in the compositions of the
invention.
The anionic surfactant herein preferably comprises at least a sulphate
surfactant and/ or a
sulphonate surfactant or mixtures thereof. It may be preferred that the
anionic surfactant
comprises only alkyl sulphonate surfactant or optionally combined with fatty
acids or
20 soap salts thereof. Alternatively, it may be preferred that the composition
comprises only
akly sulphate surfactant, but hereby it is preferred that at least a mid-chain
branched alkyl
surfactant is present or at least two alkyl surfactants are present.
Depending on the precise formulation of the composition and the use thereof,
it may be
25 preferred that the compositions herein comprise a particulate component, as
descriebd
above, preferably in the form of a flake of an alkyl sulfate or sulphonate
surfactant,
preferably an alkyl benzene sulphonate, present at a concentration of from 85%
to 95% of
the particle or flake, the balance being an sulfate salt and moisture, the
particle or flake
being admixed to the other detergent components) or ingredients.
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Other possible anionic surfactants include the isethionates such as the acyl
isethionates,
N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 1 g
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
Anionic Sulphonate Surfactant
The anionic sulphonate surfactants in accordance with the invention include
the salts of
C5-C20 linear or branched alkylbenzene sulphonates, alkyl ester sulphonates,
C6-C22
primary or secondary alkane sulphonates, C6-C24 olefin sulphonates,
sulphonated
polycarboxylic acids, and any mixtures thereof.
Highly preferred is a C 12-C 16 linear alkylbenzene sulphonate. Preferred
salts are sodium
and potassium salts.
The alkyl ester sulphonated surfactant are also suitable for the invention,
preferably those
of 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 1, and M is a cation. The counterion M is preferably
sodium,
potassium or ammonium.
The alkyl ester sulphonated 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,
CA 02344434 2004-11-04
preferably 16 C atoms and x is preferably 0. RZ is preferably ethyl or more
preferably
methyl.
It can be preferred that tlx R' of the ester is derived from unsaturated fatty
acids, with
5 preferably 1, 2 or 3 double bonds. It can also be preferred that R' of the
ester is derived
from a natural occurring fatty acid, preferably palmic acid or stearic acid or
mixtures
thereof.
Anionic Alkvl Sulphate Surfactant
The anionic sulphate surfactant herein include the linear and branched primary
and
secondary alkyl sulphates and disulphates, alkyl ethoxysulphates having an
average
ethoxylation number of 3 or below, fatty oleoyl glycerol sulphates, alkyl
phenol ethylene
oxide ether sulphates, the CS-C1~ acyl-N-(C1-C4 alkyl) and -N-(C1-C2
hydroxyalkyl)
glucamine sulphates, and sulphates of alkylpolysaccharides.
Primary alkyl sulphate surfactants are preferably selected from the linear and
branched
primary C 10-C 1 g alkyl sulphates, more preferably the C 11-C 15 linear or
branched chain
alkyl sulphates, or more preferably the C12-C14 linear chain alkyl sulphates.
Preferred secondary alkyl sulphate surfactant are of the formula
R'-CH(SO'M)-R'
wherein R3 is a Ca-C~hydrocycarbyl, R' is a hydrocycarbyl and M is a cation.
Alkyl ethoxy sulphate surfactants are preferably selected from the group
consisting of the
C 10-C 1 g alkyl sulphates which have been ethoxylated with from 0.5 to 3
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulphate
surfactant is a
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C 11-C 1 g, most preferably C 11-C 15 alkyl sulphate which has been
ethoxylated with from
0.5 to 3, preferably from 1 to 3, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulphate and alkyl ethoxysulphate surfactants. Preferred salts are sodium and
potassium
salts.
Mid-Chain Branched Anionic Surfactants
Preferred mid-chain branched primary alkyl sulfate surfactants for use herein
are of the
formula
R R1 R2
CH3CH2(CH2)~,CH(CH2)xCH(CH2)~H(CHZ)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 the
surfactant system 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.
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R, R1, and R2 are each independently selected from hydrogen and C 1-C3 alkyl
group
(preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and
most
preferably methyl), provided R, R1, and R2 are not all hydrogen. Further, when
z is 1, at
least R or R1 is not hydrogen.
M is hydrogen or a salt forming cation depending upon the method of synthesis.
w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer
from 0 to 13; z is
an integer of at least l; and w + x + y + z is an integer from 8 to 14.
A preferred mid-chain branched primary alkyl sulfate surfactant is, a C16
total carbon
primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and
having 1, 2,
or 3 branching units (i.e., R, R1 and/or R2) of in total 3 carbon atoms,
(whereby thus the
total number of carbon atoms is at least 16). Preferred branching units can be
one propyl
branching unit or three methyl branching units.
Another preferred surfactant are branched primary alkyl sulfates having the
formula
R1 R2
I I
CH3CH2(CHZ)xCH(CH2}yCH(CHz)zOS03M
wherein the total number of carbon atoms, including branching, is from 15 to
18, and
when more than one of these sulfates is present, the average total number of
carbon
atoms in the branched primary alkyl moieties having the above formula is
within the
range of greater than 14.5 to about 17.5; R1 and R2 are each independently
hydrogen or
C1-C3 alkyl; M is a water soluble cation; x is from 0 to 1 l; y is from 0 to
11; z is at least
2; and x + y + z is from 9 to 13; provided R1 and R2 are not both hydrogen.
Dianionic Surfactants
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13
The dianionic surfactants are also useful anionic surfactants for the present
invention, in
particular those of formula
AX---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 C2q., most preferably
Cg to C20,
or hydrogen; A nad B are independently selected from alkylene, aIkenylene,
(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 1; 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.
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:
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14
~OS03 M+
R~ _
~OSO 3 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 +
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; 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.
It can be preferred that the dianionic surfactants of the invention are
alkoxylated dianionic
surfactants.
The alkoxylated dianionic surfactants of the invention comprise a structural
skeleton of at
least five carbon atoms, to which two anionic substituent groups spaced at
least three
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atoms apart are attached. At least one of said anionic substituent groups is
an alkoxy-
linked sulphate or sulphonate group. Said structural skeleton can for example
comprise
any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl,
alkaryl, ether, ester,
amine and amide groups. Preferred alkoxy moieties are ethoxy, propoxy, and
5 combinations thereof.
The structural skeleton preferably comprises from 5 to 32, preferably 7 to 28,
most
preferably 12 to 24 atoms. Preferably the structural skeleton comprises only
carbon-
containing groups and more preferably comprises only hydrocarbyl groups. Most
10 preferably the structural skeleton comprises only straight or branched
chain alkyl groups.
The structural skeleton is preferably branched. Preferably at least 10 % by
weight of the
structural skeleton is branched and the branches are preferably from 1 to 5,
more
preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not
including the
15 sulphate or sulphonate group attached to the branching).
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 C 1 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 C 1 to C2g, preferably C 1 to C5, most
preferably C 1 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 1; 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
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16
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 1, both X and Y are sulfate groups, and M is a potassium,
ammonium, or a
sodium ion.
Preferred alkoxylated dianionic surfactants herein include:
ethoxylated and/or propoxylated disulphate compounds, preferably C 10-C24
straight or
branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates,
more
preferably having the formulae:
(EO/PO)n OS03 M + R
~(EO/PO)n OS03 ' M +
+ EO/PO -OSO M +
(EO/PO)m OSO 3 M ( )m 3
and
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C6 to about C 1 g; EO/PO are alkoxy moieties selected from ethoxy,
propoxy, and
mixed ethoxy/propoxy groups; and n and m are independently within the range of
from
about 0 to about 10 (preferably from about 0 to about 5), with at least m or n
being 1.
Anionic CarboxKlate 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
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17
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-
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-C 1 ~ linear or branched alkyl or alkenyl
group, R1 is
a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and
oleoyl methyl sarcosinates in the foam of their sodium salts.
Effervescence System
Any effervescence system known in the art can be used in the composition of
the
invention. A preferred effervescence system comprises an acid source, capable
of reacting
with an alkali source in the presence of water to produce a gas.
CA 02344434 2001-03-15
WO 00!18869 PCTlUS98/20221
18
The acid source is preferably present at a level of from 0.5% 0 35~%, more
preferably
from 1.0% or even 2% to 20% or even form 4% to 20% by weight of the
composition.
It may be preferred that the acid source or part thereof and the alkali source
or part thereof
are comprised in an intimate mixture, for example in the form of a compacted
particle.
The molecular ratio of the acid source to the alkali source, is preferably
from 50:1 to 1:50,
more preferably from 20:1 to 1:20 more preferably from 10:1 to 1:10, whereby
when an
intimate mixture of the acid source and the alkali source is present, this
ratio is more
preferably from 5:1 to 1:3, more preferably from 3:1 to 1:2, more preferably
from 2:1 to
1:2.
The acid source component may be any organic, mineral or inorganic acid, or a
derivative
thereof, or a mixture thereof. Preferably the acid source component comprises
an organic
acid.
The acid compound is preferably substantially anhydrous or non-hygroscopic and
the acid
is preferably water-soluble. It may be preferred that the acid source is
overdried.
Suitable acids source components include citric, malic, malefic, fiunaric,
aspartic,
glutaric, tartaric succinic or adipic acid, monosodium phosphate, boric acid,
or derivative
thereof. Citric acid, malefic or malic acid are especially preferred.
Most preferably, the acid source provides acidic compounds which have an
average
particle size in the range of from about 75 microns to 1180 microns, more
preferably from
150 microns to about 710 microns, calculated by sieving a sample of the source
of acidity
on a series of Tyler sieves.
As discussed above, the effervescence system preferably comprises an alkali
source,
however, for the purpose of the invention, it should be understood that the
alkali source
may be part of the effervescence particle or can be part of the cleaning
composition
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WO 00/18869 PCT/US98/24221
19
comprising the particle, or can be present in the washing liquor, whereto the
particle or
the cleaning composition is added.
Any alkali source which has the capacity to react with the acid source to
produce a gas
may be present in the particle, which may be any gas known in the art,
including nitrogen
ogygen and carbondioxide gas. Preferred can be perhydrate bleaches, including
perborate,
and silicate material. The alkali source is preferably substantially anhydrous
or non-
hydroscopic. It may be preferred that the alkali source is overdried.
Preferably this gas is carbon dioxide, and therefore the alkali source is a
preferably a
source of carbonate, which can be any source of carbonate known in the art. In
a preferred
embodiment, the carbonate source is a carbonate salt. Examples of preferred
carbonates
are the alkaline earth and alkali metal carbonates, including sodium or
potassium
carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with
ultra-fine
calcium carbonate such as are disclosed in German Patent Application No.
2,321,001
published on November 15, 1973. Alkali metal percarbonate salts are also
suitable
sources of carbonate species, which may be present combined with one or more
other
carbonate sources.
The carbonate and bicarbonate preferably have an amorphous structure. The
carbonate
and/ or bicarbonates may be coated with coating materials. It can be
preferered that the
particles of carbonate and bicarbonate can have a mean particle size of 75
microns or
preferably 150pm or greater, more preferably of 250~.m or greater, preferably
SOOpm or
greater. It may be preferred that the carbonate salt is such that fewer than
20% (by weight)
of the particles have a particle size below SOO~,m, calculated by sieving a
sample of the
carbonate or bicarbonate on a series of Tyler sieves. Alternatively or in
addition to the
previous carbonate salt, it may be preferred that the fewer than 60% or even
25% of the
particles have a particle size below 150~m, whilst fewer than 5% has a
particle size of
more than 1.18 mm, more preferably fewer than 20% have a particle size of more
than
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212 pm, calculated by sieving a sample of the. carbonate or bicarbonate on a
series of
Tyler sieves.
Additional Ingredients
The compositions herein may contain additional detergent components. The
precise
nature of these additional components, and levels of incorporation thereof
will depend on
the physical form of the compositions comprising the builder component and the
precise
nature of the washing operation for which it is to be used.
10 Additional ingredients include additional builders, additional surfactants,
bleach,
enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-
redeposition
agents soil releasing agents, perfumes, brightners, photobleaching agents and
additional
corrosion inhibitors.
15 Water-Soluble or PartiallX Water-Soluble Builders
The composition preferably comprises one or mare water-soluble or partially
water-
soluble builders.
20 These include crystalline layered silicates an organic carboxylates or
carboxylic acids.
The preferred crystalline layered silicate herein have the general formula
NaMSix02x+1 ~YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0
to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-
0164514
and methods for their preparation are disclosed in DE-A-3417649 and DE-A-
3742043.
For the purpose of the present invention, x in the general formula above has a
value of 2,
3 or 4 and is preferably 2. M is preferably H, K or Na or mixtures thereof,
preferably Na.
The most preferred material is a-Na2Si205~ ~_ Na2Si205 or s-Na2Si205, or
mixtures
CA 02344434 2004-11-04
. 21
thereof, preferably being at least 75% Na2Si205, for example available from
Clariant as
NaSKS-6T"''.
The crystalline layered silicate material, in particular of the formula
Na2Si205
may optionally comprise other elements such as B, P, S, for example obtained
by
processes as described in EP 578986-B.
The crystalline layered silicate may be in an intimate mixture with other
materials,
including one or more of surfactants of the surfactant system herein.
Preferred other
materials are other water-soluble builders, including (poly) carboxylic acids
and salts
thereof, including polymeric compounds such as acrylic and/ or malefic acid
polymers,
inorganic acids or salts, including carbonates and sulphates, or small levels
of other
silicate material, including amorphous silicate, meta silicates, and
aluminosilicates, as
described herein.
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their
salts in which the polycarboxylic acid comprises at least two carboxylic
radicals separated
from each other by not more that two carbon atoms 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. In addition to these water-soluble builders, polymeric
polycarboxyltes may
be present, including homo and copolymers of malefic acid and acrylic acid and
their salts.
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.
CA 02344434 2004-11-04
22
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates, aconitrates and citraconates as well as succinate derivatives such
as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates
described in British Patent No. 1,389,732, and aminosuccinates described in
Canadian
Patent No. 973771, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-
propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. PolycarboxyIates
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
pymlysed
citrates described in British Patent No. 1,439,000. Preferred polycarboxylates
are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly citrates.
Most preferred may be citric acid, malic acid, and fumaric acid, or their
salts or mixtures
thereof.
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.
Alkox,~lated Nonionic Surfactant
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 ethoxyiated alcohols, nonionic
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23
ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates
with propylene glycol, and the nonionic ethoxylate condensation products with
propylene
oxide/ethylene diamine adducts.
Nonionic Alkox~ated Alcohol Surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are suitable for
use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or
secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred are
the condensation products of alcohols having an alkyl group containing from 8
to 20
carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic Pol~hydroxY Fattv Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy
propyl, ethoxy, propoxy, or a mixture thereof, preferable C 1-C4 alkyl, more
preferably C 1
or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a CS-C31
hydrocarbyl,
preferably straight-chain CS-C 1 g alkyl or alkenyl, more preferably straight-
chain Cg-C 1 ~
alkyl or alkenyl, most preferably straight-chain C 11-C 1 ~ alkyl or alkenyl,
or mixture
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at
least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably
ethoxylated or propoxylated) thereof. Z preferably will be derived from a
reducing sugar
in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic Fattv Acid Amide Surfactant
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24
Suitable fatty acid amide surfactants include those having the formula:
R6CON(R7)2
wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17
carbon
atoms and each R7 is selected from the group consisting of hydrogen, CI-C4
alkyl, C1-
C4 hydroxyalkyl, and -(C2H4O)xH, where x is in the range of from 1 to 3.
Nonionic Alkylpolvsaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued 3anuary 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 I.3 to 8. The
glycosyl is
preferably derived from glucose.
Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the
alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
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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
5 alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
10 Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions 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,
15 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
2o is a C6-Clg hydrocarbyl group, each R1 is typically Cl-C3 alkyl, and R2 is
a Cl-CS
hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
25 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
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26
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 compositions 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-alkox~ated amine surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant
preferably of the
general formula I:
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WO 00/18869 PCT/US98/20221
27
R\ /ApRa
2 /N 'R3 X-
R / (I)
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to
about 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 --0H group is separated from the
quaternary
ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred
ApR4
groups are --CH2CH20H, ~H2CH2CH20H, --CH2CH(CH3)OH and -
CH(CH3)CH20H, with-~H2CH20H being particularly preferred. Preferred R1 groups
are linear alkyl groups. Linear R 1 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
R\ /(CH2CH20)2-SH
\N+/ XO
CH3/ \CH3
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28
wherein R 1 is C 10-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
compositions of the invention is preferably from 0.1 % to 20%, more preferably
from
0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
Cationic Bis-Alkoxylated Amine Surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general
formula II:
R1 /ApRs
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-Cq. alkoxy, especially ethoxy, (i.e., -CH2CH20-),
propoxy, butoxy
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29
and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q
is from 1 to
about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
+/CHZCH20H
~N X
CH3/ \CH2CH20H
wherein R 1 is C l 0-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-
Clq, alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each
monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include
compounds of the
formula:
R~ ~(CH2CH20)pH
N+ X-
R2~ ~(CH2CH20)qH
wherein R 1 is C l 0-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 Cl-C3 alkyl, preferably methyl, and X is
an anion,
especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20)
units {EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20] and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr
and/or
i-Pr units.
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Perh~drate Bleaches
A highly preferred additional components of the compositions herein is an
oxygen bleach,
5 preferably comprising a hydrogen peroxide source and a bleach precursor or
activator.
A prferred source of hydrogen peroxide is a perhydrate bleach, such as metal
perborates,
more preferably metal percarbonates, particularly the sodium salts. Perborate
can be mono
or tetra hydrated. Sodium percarbonate has the formula corresponding to
10 2Na2C03.3H202, and is available commercially as a crystalline solid.
In particular the percarbonate salts are preferably coated. Suitable coating
agent are
known in the art, and include silicates, magnesium salts and carbonates salts.
15 Potassium peroxymonopersulfate, sodium per is another optional inorganic
perhydrate
salt of use in the detergent compositions herein.
Organic Peroxyacid Bleaching System
20 A preferred feature of the composition herein 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,
25 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.
30 Perox~acid Bleach Precursor
CA 02344434 2004-11-04
_31
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
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
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.
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32
Leaving Groups
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis
reaction to occur within the optimum time frame (e.g., a wash cycle). However,
if L is too
reactive, this activator will be difficult to stabilize for use in a bleaching
composition.
Preferred L groups are selected from the group consisting of:
Y R3 RaY
-O ~ , -O ~ Y , and -O
1 O 4
-N-C-R -N N -N-C-CH-R
R3 ~ ~ R3 Y
I
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
~ '
O Y O
O C H2-C
_~C-R1 -N\C/NR4 ' _N\C/NR ,
p O
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33
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
R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be
substituted by
essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03-M+, -C02-M+, -S04 M+, -N+(R3)4X and
O<--N(R3)3 and most preferably -S03 M+ and -C02 M+ wherein R3 is an alkyl
chain
containing from 1 to 4 carbon atoms, M is a canon which provides solubility to
the bleach
activator and X is an anion which provides solubility to the bleach activator.
Preferably,
M is an alkali metal, ammonium or substituted ammonium cation, with sodium and
potassium being most preferred, and X is a halide, hydroxide, methylsulfate or
acetate
anion.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
,N,N 1 N 1 tetra acetylated alkylene diamines wherein the alkylene group
contains from 1
to 6 carbon atoms, particularly those compounds in which the alkylene group
contains 1,
2 and 6 carbon atoms. Tetraacetyi ethylene diamine (TAED) is particularly
preferred. The
CA 02344434 2004-11-04
34
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 Plk 1~ Peroxvacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ -C-N-RZ-C-L R~ -N-C-R2-C-L
R5 OI or R5 !O 10
wherein Rl is an alkyl gmup with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing fmm 1 to 14 carbon atoms, and RS is H or an alkyl group containing
1 to 10
carbon atoms and L can be essentially any leaving group. Amide substituted
bleach
activator compounds of this type are described is 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 benzoylatiag agents, and those of the imide
type
including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-
benzoyl
substituted areas. Suitable imidazole type perbenzoic acid precursors include
N-benzoyl
imidazole and N-benzoyl benzimidazole. Other useful N-aryl group-containing
CA 02344434 2004-11-04
perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine
and benzoyl
pyroglutamic acid.
5 Preformed Organic Peroxyacid
The detergent composition may contain, in addition to, or as an alternative
to, an organic
peroxyacid bleach precursor compound, a prefon~ned organic peroxyacid ,
typically at a
level of from 1 % to 15% by weight, more preferably from I% to I O% by weight
of the
10 composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
R~ -C- -R2-C-OOH R~ - -R2- -OOH
il ~ II ~ I
15 O R5 O or R5
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and R~ is
H or an alkyl, aryl, or alkaryl gmup containing 1 to 10 carbon atoms. Amide
substituted
20 organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc
acid. Mono- and diperazelaic acid, mono- and diperbrassyiic acid and N-
25 phthaloylaminoperoxicaproic acid are also suitable herein.
Heaw Metal Ion Se~uestrant
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WO 00/18869 PCT/US98/20221
36
Heavy metal ion sequestrant are also useful additional ingredients herein. By
heavy metal
ion sequestrant it is meant herein components which act to sequester (chelate)
heavy
metal ions. These components may also have a limited calcium and magnesium
chelation
capacity, but preferentially they show selectivity to binding heavy metal ions
such as iron,
manganese and copper. The are thus not considered builders for the purpose of
the
invention.
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.
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, 1,1
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-hydroxypropylenediarnine
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
described in EP-A-516,102 are also suitable herein. The ~3-alanine-N,N'-
diacetic acid,
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WO 00/18869 PCT/US98/20221
37
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.
Enzyme
Another preferred ingredient useful 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.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the
compositions
herein.
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WO 00/18869 PCT/US98/20221
38
By organic polymeric compound it is meant herein essentially any polymeric
organic
compound commonly used as binder, dispersants, and anti-redeposition and soil
suspension agents in detergent compositions, including any of the high
molecular weight
organic polymeric compounds described as clay flocculating agents herein,
including
quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition
agent.
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.
CA 02344434 2004-11-04
39
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.
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 Canadian Patent Application
No. 2,295,214.
Another organic compound, which is a preferred clay dispersant/ anti-
redeposition agent,
for use herein, can be the ethoxylated cationic monoamines and diamines of the
formula:
~'H3 ( H3
X - f - OCH2CH2)n I~ -- CH2 - CH2 -f- CH2)a b I~ - CH2CH20 ?n X
(CH2CH20 ~ X (CH2CH20 ~ X
wherein X is a nonionic gmup selected from the group consisting of H, C 1-C4
alkyl or
hydmxyalkyl 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~), 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.
2o Other dispersants/ anti-redeposition agents for use herein are described in
EP-B-Ol 1965
and US 4,659,802 and US 4,664,848.
Suds Suppressing System
The detergent compositions of the invention, when formulated for use in
machine
washing compositions, may comprise a suds suppressing system present at a
level of from
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WO 00/18869 PCT/US98/20221
0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3%
by
weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
5 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
10 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
15 "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.
20 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, far
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,
25 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-C4p ketones (e.g. stearone) N-alkylated amino triazines such as tri- to
hexa-
30 alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as
products of cyanuric
' CA 02344434 2004-11-04
. 41
chloride with two or three moles of a primary or secondary amine containing 1
to 24
carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-
alkali metal
(e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A°preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from SO% 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~/0, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%,
preferably 1% to 10% by weight; a particularly preferred silicone glycol rake
copolymer of this type is DC0544T"', commercially available from DOW Corning
under the trade mark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C 18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to
15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
CA 02344434 2001-03-15
WO 00/18869 PCTNS98/20221
42
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and
comprises a silicone antifoam compound and an organic carrier material having
a melting
point in the range 50°C to 85°C, wherein the organic carrier
material comprises a
monoester of glycerol and a fatty acid having a carbon chain containing from
12 to 20
carbon atoms. EP-A-0210721 discloses other preferred particulate suds
suppressing
systems wherein the organic carrier material is a fatty acid or alcohol having
a carbon
chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a
melting point of
from 45°C to 80°C.
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.
Polymeric Dye Transfer Inhibiting Agents
The compositions herein may also comprise from 0.01% to 10 %, preferably from
0.05%
to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinyipyrrolidonepolymers or combinations thereof, whereby these polymers
can be
cross-linked polymers.
Optical Brightener
The compositions herein also optionally contain from about 0.005% to 5% by
weight of
certain types of hydrophilic optical brighteners, as known in the art.
CA 02344434 2001-03-15
WO 00/18869 PCT/US98/20221
43
Polymeric Soil Release A;~ent
Polymeric soil release agents, hereinafter "SRA", can optionally be employed
in the
present compositions. 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.
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 occurring 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
' CA 02344434 2004-11-04
44
poly(ethyleneglycol) ("PEG"). Other examples of SRA'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
~ulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31,
1989 to
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
furnher
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 C1-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 marks of methyl cellulose ethers manufactured by
Shin-etsu
Kagaku Kogyo KK.
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
CA 02344434 2004-11-04
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:
5 (III) anionic terephthalate-based SR.A's of the urethane-linked variety, see
U.S. 4,201,824,
Violland et al.;
Other Optional Ingredients
10 Other optional ingredients suitable for inclusion in the compositions of
the invention
include perfumes, speckles, colours or dyes, filler salts, with sodium sulfate
being a
preferred filler salt.
Also, minor amounts (e.g., less than about 20% by weight) of neutralizing
agents,
t5 buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents,
polyacids, suds
regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those
described in US
Patent 4,285,841 to Barrat et al., issued August 25, 1981
can be present.
20 Highly preferred are encapsulated perfumes, preferably comprising a starch
encapsulte.
In the compositions of the invention, it may be preferred that when dyes and/
or perfiunes
are sprayed onto the another component, the component does not comprise spray-
on
nonionic alkoxylated alcohol surfactant.
Form of the Compositions
The composition of the invention thereof can be made via a variety of methods
involving
the mixing of ingredients, including dry-mixing, compaction such as
agglomerating,
extrusion, tabletting, or spray-drying of the various compounds comprised in
the
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WO 00/18869 PCT/US98/20221
46
detergent component, or mixtures of these techniques, whereby the components
herein
also can be made by for example compaction, including extrusion and
agglomerating, or
spray-drying.
The compositions herein can take a variety of physical solid forms including
forms such
as tablet, flake, pastille and bar, and preferably the composition is in the
form of granules
or a tablet.
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.
The compositions preferably have a density of more than 350 gr/litre, more
preferably
more than 450 gr/litre or even more than 570 gr/litre.
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47
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
LAS : Sodium linear C11-13 alkyl benzene sulfonate
LAS (I) : Flake containing sodium linear C11-13 alkyl
benzene
sulfonate (90%) and sodium sulphate and moisture
LAS(II) . Potassium linear C11-13 alkyl benzene sulfonate
MES : a-sulpho methylester of C,8 fatty acid
TAS : Sodium tallow alkyl sulfate
CxyAS : Sodium C 1 x - C 1 y alkyl sulfate
C46SAS : Sodium C 14 - C 16 secondary (2,3) alkyl sulfate
CxyEzS . Sodium C 1 x-C 1 y 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(C2H40H) with R2 = C12 - C14
QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = Cg - C11
SADS : Sodium C,4-CZZ alkyl disulfate of formula
2-(R).C4 H,.-1,4-
(S04-)2 where R = C,~C,g
SADE2S : Sodium C,4-C22 alkyl disulfate of formula
2-(R).C4 H,.-1,4-
(S04-)2 where R = C,o C,B, condensed with z
moles of
ethylene oxide
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
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WO 00/18869 PCT/US98/20221
48
CFAA : C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA : C I 6-C I g alkyl N-methyl glucamide
TPKFA : C 16_C 1 g topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(Al02Si02)12~27H20 having a primary particle size
in the range from 0.1 to 10 micrometers (weight expressed
on an anhydrous basis)
NaSKS-6 (I) : Crystalline layered silicate of formula 8- Na2Si205 of
weight average particle size of 18 microns and at least 90%
by weight being of particle size of below 65.6 microns.
NaSKS-6 (II) : Crystalline layered silicate of formula 8- Na2Si205 of
weight average particle size of 18 microns and at least 90%
by weight being of particle size of below 42.1
microns.
Citric acid : Anhydrous citric acid
Borate : Sodium borate
Carbonate : Anydrous sodium carbonate with a particle
size between
200~m and 900~,m
Bicarbonate . Anhydrous sodium bicarbonate with a particle
size
distribution between 400~tm and 1200~m
Silicate . Amorphous sodium silicate (Si02:Na20 = 2.0:1
)
Sulfate : Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a
particle size distribution between 425~m and 850~m
MA/AA : Copolymer of I :4 maleic/acrylic acid, average molecular
weight about 70,000
CA 02344434 2004-11-04
49
MA/AA ( 1 ) . Copolymer of 4:6 maleic/acrylic acid, average
molecular
weight about 10,000
pA . 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
trade mark 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 enzyiize, 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
trade mark Carezyme
Amylase . Amylolytic enzyme, having 1.6% by weight of
active
enzyme, sold by NOVO Industries A/S under
the
trade mark 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
trade mark Lipolase
Lipase ( 1 ) . Lipolytic enzyme, having 2.0% by weight of
active
enzyme, sold by NOVO Industries A/S under
the
trade mark Lipolase Ultra
Endolase . Endoglucanase enzyme, having 1.5% by weight
of active
enzyme, sold by NOVO Industries A/S
CA 02344434 2004-11-04
pg4 . Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
pBl : Anhydrous sodium perborate bleach of nominal
formula
NaB02.H202
5 Percarbonate . Sodium percarbonate of nominal formula
2Na2C03.3H20~
DOBS : Decanoyl oxybenzene sulfonate in the form
of the sodium
salt
DPDA ~ . Diperoxydodecanedioc acid
10 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
15 DOBS . Decanoyloxybenzene sulfonate in the form
of the
sodium salt
DOBA . Decanoyl oxybenzoic acid
TAED . Tetraacetylethylenediamine
DTPA . Diethylene triamine pentaacetic acid
20 DTPMP . Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under the trade mark
bequest 2060
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S)
isomer in the
form of its sodium salt.
Photoactivated bleach:Sulfonated zinc phthlocyanine or sulfonated
alumino
25 phthlocyanine encapsulated in or carried
by a 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
30 HEDP . I,l-hydroxyethane diphosphonic acid
r
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. 51
PEGx : Polyethylene glycol, with a molecular weight
of x
(typically 4,000)
PEO . Polyethylene oxide, with an average molecular
weight of
50,000
TEPAE : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidosole, with an average molecular
weight of
20,000
pVp . Polyvinylpyrolidone polymer, with an average
molecular
weight of 60,000
PVNO : Polyvinylpyridine N-oxide polymer, with an
average
molecular weight of 50,000
PVPVI . Copolymer of polyvinylpyrrolidone 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
SRP 1 : Anionically end capped polyesters
SRP 2 : Diethoxylated poly (1, 2 propylene terephthalate)
short
block polymer
PEl : Polyethyleneimine with an average molecular
weight of
1800 and an average ethoxylation degree of
7 ethyleneoxy
residues per nitrogen
Silicone antifoam Polydimethylsiloxane foam controller with
: siloxane-
oxyalkylene copolymer as dispersing agent
with a ratio of
said foam controller to said dispersing agent
of 10:1 to
100:1
Opacifier : Water based monostyrene latex mixture, sold
by BASF
Aktiengesellschaft under the trade mark Lytron
621
Wax . Parai~n wax
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52
Example I
A B C D E F G H I
Blown powder
LAS 5.0 8.0 3.0 5.0 5.0 10.0 - - -
TAS - 1.0 - - - -
MBAS - - 5.0 S.0 - - -
C45AS - - 1.0 2.0 2.0 - - -
C45AE3S - - 1.0 - - -
QAS 1.0 1.0 - - -
DTPA, HEDP 0.3 0.3 0.5 0.3 - - -
and/
or EDDS
MgS04 0.5 0.5 0.1 - - - -
Sodium citrate- - - 3.0 5.0 - - -
Sodium carbonate10.0 7.0 15.0 10.0 - - -
Sodium sulphate5.0 5.0 - - 5.0 3.0 - - -
Sodium silicate- - - - 2.0 - - -
1.6R
Zeolite A 16.0 18.0 20.0 - - - - - -
SKS-6 - - - 3.0 S.0 - - - -
MA/AA or AA 1.0 2.0 11.0 - - 2.0 - - -
PEG 4000 - 2.0 - 1.0 - 1.0 - - -
QEA 1.0 - - - 1.0 - - - -
Brightener 0.05 0.05 0.05 - 0. 05 - - - -
Silicone oil 0.01 0.01 0.01 - - 0.01 - - -
Agglomerate
LAS - - - - - 2.0 -
MBAS - - - - 2.0 - 1.0
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C24AE3 - - - - 1.0 0.5
Carbonate - - - 1.0 1.0 1.0 -
Sodium citrate - - - - - - S.0
CFAA - 2.0 - - 2.0
QAS - - - 1.0 - 1.0 1.0
QEA - - - 2.0 2.0 1.0 -
SRP - - - 1.0 1.0 0.2 -
Zeolite A - - - 10.026. 15.016.0
0
Sodium silicate - - - - - - -
PEG - - - - - - 4.0 - -
A~~lomerates
SKS-6 6.0 8.0 - - 6.0 3.0 - 7.0 10.0
LAS 4.0 5.0 - - 5.0 3.0 - 10.012.0
Dry-add particulate
components
Malefic 8.0 10.0 10.0 4.0 - 8.0 2.0 2.0 4.0
acid/carbonate/bica
rbonate
(40:20:40)
QEA - - - 0.2 0.5 - - - -
NACAOBS 3.0 - - 1.5 - - - 2.5 -
NOBS - 3.0 3.0 - - - - - 5.0
TAED 2. - - 1. 2.5 6. - 1. -
S 5 5 5
MBAS - - - 8.0 - - 8.0 - 4.0
LAS (I) 10.0 10.0 10.0 - - - 12. 8.0 -
0
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Spray on
Brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 -
Dye - - - 0.3 0.05 0.1 - - -
7 - _ _ _ _ 0.5 - 0.7 -
Perfume - - - 0.8 - 0.5 - 0.5 -
Dry-add
Citrate - - 20.0 4.0 - 5.0 1 - 5.0
S.
0
Percarbonate 15.0 3.0 6.0 10.0- - - 18.0 5.0
Perborate - - - - 6.0 18.0 - - -
Photobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03
Enzymes 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2
(cellulase,
amylase, protease,
lipase)
Zeolite A - - - 10.010.0 - - - -
Carbonate 0.0 10.0 - - - 5.0 8.0 10.0 5.0
Perfume 0.6 0.5 0.5 - 0.3 0.5 0.2 0.1 0.6
(encapsulated)
Suds suppressor1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2
Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 -
Citric acid - - - 6.0 6.0 - - - 5.0
Dyed carboanate0.5 0.5 1.0 2.0 - 0.5 0.5 0.5 1.0
(blue, green)
SKS-6 - - - 4.0 - - - 6.0 -
Fillers up to
100%
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Example 2
The following are detergent formulations according to the present invention:
J K L M
Blown Powder
Zeolite A 12.0 20.0 - -
Sodium sulfate - 5.0 2.0 -
LAS - 10.0 3.0 -
C45AS - 4.0 4.0 -
QAS - - 1.5 -
DTPA/HEDP/EDDS 0.4 0.4 0.4 -
CMC 0.4 0.4 0.4 -
Carbonate - - 3.0
AA or MA/AA 4.0 2.0 10.0 -
Agglomerates
QAS 1.0 - - -
LAS 1.0 - 2.0 10.0
TAS - - - 1.0
Silicate 1.0 - - 0.3
Zeolite A 8.0 - 8.0 3.0
Carbonate 8.0 - 4.0 3.0
Agglomerate
NaSKS-6 15.0 12.0 - 10.0
LAS 8.0 13.0 - 8.0
AS 5.0 - -
Spray On
Perfume 0.3 0.3 0.3 0.5
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Brightener 0.01 0.01 0.01 0.01
C25E5 2.0 - 1.0 -
Dry additives
LAS (I) - - 7.0 -
QEA 1.0 0.5 0.5 0.5
Citrate - - 10.0 -
Bicarbonate - 3.0 -
Carbonate 8.0 15.0 10.0
NAC OBS 4.0 - - -
TAED 2.0 - 0.3 5.0
NOBS - 2.0 3.0
PC/PB 1 14.0 3.0 3.0 18.0
PEG - - 0.9 0.5
Soap - 0.5 - -
Malic acid 7.0 - - -
Zeolite A 2.0 - - -
Polyethylene oxide - - - -
of MW
5,000,000
Citric acid - - - 5.0
Protease 1.0 0.5 0.3 0.5
Lipase - 0.4 - -
Amylase 0.6 0.6 0.6
Zeolite A - - 16.0 10.0
Cellulase 0.6 0.2 - 0.3
SKS-6 - - 10.0 -
_ sue, 0.1 0.1 0.1 0.1
CMC - 0.3 - 0.5
_ pVP - - 0.1 0.2
Silicone antifoam 0.5 1.5 1.0 0.3
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Sodium sulfate 0.0 3.0 0.0 -
Balance (Moisture 100.0 100.0 100.0
and
Miscellaneous)
Density (g/litre) 800 600 700 850
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S8
Example 3
The following are detergent formulations according to the present invention:
N O P R
Agglomerate
QAS 2.0 - 2.0 -
MES - 2.0 - -
LAS (II) 6.0 - - -
C4SAS 6.0 4.0 2.0 -
MBAS 16.5, 1.9 4.0 - - -
Zeolite A - 6.0 8.0 8.0
Carbonate 4.0 8.0 - 8.0
MA/AA 4.0 2.0 2.0 6.0
CMC O.S 0.5 1.0 O.S
DTPMP 0.4 0.4 - O.S
Spray On
C2SE3 1.0 1.0 - -
Perfume O.S O.S O.S O.S
Agglomerate
SKS-6 7.0 1 S.0 1 S.0 10.0
LAS 3.0 9.0 1 S.0 10.0
Zeolite 1 S.0 - - -
C4S AS - 3.0 - -
Dry Adds
LAS (I) - - - 1 S.0
EDDS/HEDP O.S 0.3 O.S 0.8
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Zeolite A 3.0 12.0 5.0 3.0
NaSKS 6 - - - 11.0
Citrate - 1.0 - -
Citric acid 2.0 - 2.0 4.0
NAC OB S 4.1 - 5.0 4.0
TAED 0.8 2.0 - 2.0
Percarbonate 20.0 20.0 1 S.0 17.0
SRP 1 0.3 0.3 - 0.3
Protease 1.4 1.4 1.0 0.5
Lipase 0.4 0.4 0.3 -
Cellulase 0.6 0.6 0.5 0.5
Amylase 0.6 0.6 - 0.3
QEA 1.0 - 1.0 1.0
Silicone antifoam 1.0 0.5 0.5 1.5
Brightener 1 0.2 0.2 - 6.2
Brightener 2 0.2 - 0.2 -
Density (g/litre) 850 850 800 775
