Note: Descriptions are shown in the official language in which they were submitted.
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Builder component
Technical field
The invention relates to builder components which have an excellent building
performance an improved dispensing and dissolution and which are in particular
useful
for detergent compositions.
Background to the Invention
In the past decades detergent manufacturers have been focused on the
development of
improved builders as alternatives to phosphate builders. On one hand, new
builder
materials have been developed and on the other hand existing builders or
builder
combinations have been improved, for example by optimizing the levels or
ratios of the
builder materials. In general, most detergents still employ polycarboxylate
builders and
silicate builders, such as aluminosilicates, amorphous and crystalline sodium
silicates.
It has been found that one of the main complaints of the users of detergent
products is
that the products do not always dispense satisfactory. This results in
residues of the
product in the dispensing drawer, for example in the form of a gel, in the
washing
machine and also on the fabrics after the wash. This can be in particular a
problem with
certain ingredients or with high density products, under cold water washing
conditions or
when limited amounts of water are used in the washing process, such as the
case in the
initial phase of the washing process when small amounts of water contact the
product in
the dispensing drawer or in the interior of the machine.
A problem related to the gelling of the product is that the product is not
delivered
e~ciently to the wash because not only the gelling ingredients do not dispense
well, also
the product trapped in the gel is not dispensed well, whereby these
ingredients can not
contribute to the cleaning performance. Furthermore, the incorporation in
detergents of
certain ingredients which have a tendency to gel or cake have a negative
impact on the
flowability of the product.
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Another problem associated with certain detergent ingredients is that they do
not always
dissolve satisfactory, for example aluminosiiicates, amorphous silicates,
coarse silicate
materials. This may result in a reduced cleaning performance or deposition of
product on
the fabric or the washing machine.
The inventors have now found that often those ingredients which dispense well,
do not
dissolve satisfactory and have a tendency to deposit and form residues on the
fabrics in
the wash. On the other hand, ingredients which dissolve well, have a tendency
to gel
upon initial contact with water.
The inventors have now found that a builder component, containing a ground
crystalline
layered silicate material whereof the particles have a particle size of less
than about 100
microns and having a weight average particle size of more than about 1 S
microns
dissolves readily and provides excellent building. Preferably, the builder
component is
also such that 90% by weight of the particle has a particle size of from 17.3
to 88.2.
They have found that detergent compositions comprising this builder component
have an
improved flowability, an improved dispensing, a reduced gelling and a less
product
residues in the dispensing device, in the washing machine and on the fabrics,
compared
to other silicate materials, such as materials of larger particle size,
smaller particle size,
aluminosilicates, amorphous materials, or non-layered materials. It is
believed that that
the layered structure is essential to reduce the formation of gels, whilst the
particle size is
essential to provide a product which both dispenses and dissolves whilst
having a good
flowability. Furthermore, it is believed that the ground material has a
modified surface
structure whereby improved building and dispensing are achieved.
Furthermore, it has been found that the intimately mixing this crystalline
layered silicate
material with other detergent ingredients which have a tendency to form
residues or gel,
such as surfactants, in particularly anionic surfactant, reduces the formation
of residues
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or the gelling of the ingredients and thus improves the dispensing and the
e~ciency
cleaning performance of ingredients.
Summary of the Invention
The invention provides a builder component comprising a ground crystalline
layered
silicate which comprises at least 95% or even 98% or even 100% by weight
crystalline
layered silicate having a particle size of less than 150 microns or even 102
microns,
whilst having a weight average particle size of more than 15.0 microns,
preferably from
16.0 to 48.8 microns.
The builder component is in particular useful in solid detergent compositions,
in
particular solid laundry and dish washing detergent compositions.
The invention also relates to the use of a builder system comprising a ground
crystalline
layered silicate which comprises at least 95% or even 98% or even 100% by
weight of
crystalline layered silicate having a particle size of less than 1 SO microns
or even 102
microns, whilst having a weight average particle size of more than 1 S.0
microns,
preferably from 16.0 to 48.8 microns, in a detergent composition, comprising a
surfactant
and other detergent components, for improving the dispensing of the detergent
component.
Detailed Description of the Invention
The builder component
Crystalline layered silicate
The ground crystalline layered silicate of the builder component of the
invention
comprises at least 95% or even 98% or even 100% by weight of the crystalline
layered
silicate has a particle size of less than 150 microns or even 102 microns or
even less than
88.2 microns or even less than 65.6 microns, whilst having a weight average
particle size
of more than 15.0 microns, preferably from 16.0 to 48.8 microns or even from
17.3 to
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42.1 microns, as measured with a Malvern Instruments SB.OC light scattering
equipment, as descibed in the Malvern Instrument users manual.
Preferably, when the weight average particle is from 16.0 to 48.8 microns, at
least 90%
by weight of the particle has a particle size of from 17.3 to 88.2 and when
the weight
average particle is from 17.3 to 42.1 microns, at least 90% by weight of the
particle has a
particle size of from 23.3 to 76.0, as measured with a Malvern Instruments
SB.OC light
scattering equipment.
The ground material may be obtained by any method of grinding, preferably by
grinding
crystalline layered silicate material of a larger particle size than the
material of the
invention in an ceramic ball mill or an air jet mill.
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
thereof, preferably being at least 75% Na2Si205~ for example available from
Clariant as
NaSKS-6.
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.
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The component of the invention may comprise other detergent builders or other
detergent ingredients, as described herein. Typically, the builder component
may
comprise up to 85% or preferably 75% or 50% of other ingredients. Hereby, it
may be
preferred that the builder component of the invention comprises an intimate
mixture of
the crystalline layered silicate with other ingredients. When used herein,
'intimately
mixing/ mixed' or 'intimate mixture' means for the purpose of the invention
that
components of the particle are substantially homogeneously divided in the
particle.
The intimate mixture can be obtained by any process involving the mixing of
the
components, which can be part of spray-drying process, a tableting process,
extrusion
process and granulation processes including agglomeration processes. Hereby,
preferably a first step comprises forming a mixture of the crystalline layered
silicate and
the other ingredients, including preferably surfactants and granulation of the
mixture to
form a particle.
The intimately mixing step is preferably done by agglomerating the surfactant
and the
crystalline layered silicate. This may be done by any conventional
agglomeration
process. Thus, the builder component may preferably be in the form of an
agglomerate.
Preferred materials are organic acids or salts, including (poly) carboxylic
acids and salts
thereof, including polymeric compounds such as acrylic and/ or malefic acid
polymers,
polymeric compounds, inorganic acids or salts, including carbonates and
sulphates, other
silicate material, including amorphous silicate, meta silicates, other
crystalline layered
silicates and aluminosilicates, as described herein.
Preferred may be that the builder component of the invention comprises at
least a
surfactant, preferably comprising at least an anionic surfactant, as described
hereinafter.
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It may be preferred that the particle comprising of from 10% to 60% by weight,
preferably from 20% to 50% or even 35% to 45% of other ingredients and from
35% to
90%, preferably form 40% to 80% or even 45% to b5% of the crystalline layered
silicate.
It may be preferred that the other ingredient comprises a surfactant.
Preferably, the
weight ratio of the crystalline layered silicate to the surfactant in the
builder component
is from 4:5 to 7:3, more preferably from 1:1 to 2:1, most preferably from 5:4
to 3:2.
It may be preferred that the builder component comprising less than 10% by
weight,
preferably less than S% by weight of free moisture. The free moisture content
as used
herein, can be determined by placing 5 grams of the builder compoennt in a
petri dish
and placing this petri dish in a convection oven at 50°C for 2 hours,
and subsequently
measuring the weight loss, due to water evaporation.
It may be preferred that the intimate mixture comprises polymeric binder
material.
Hereby, it is preferred to use as little binder material as possible. It may
be preferred that
the intimate mixture comprises less than 25%, preferably less than 10%, more
preferably
less than S% by weight, most preferably 0% by weight of ethylene oxide
polymers.
It may be preferred that the builder component is present in a detergent
compositions.
Hereby, it may be preferred that the builder composition is present in the
form of a
separate particle, preferably an agglomerate, preferably having a weight
average particle
size of from 150 microns to 1700 microns, or more preferably 80% by weight of
the
particles has an particle size of more than 300 microns (80% by weight on
Tyler sieve
mesh 48) and less than 10% by weight of the particles has a particle size of
more than
i 180 microns (on Tyler mesh sieve 14) or even 710 microns (on Tyler mesh
sieve 24).
The detergent composition may have any form, including aqueous and non-aqueous
liquids, but preferably the composition is a solid composition in the form of
bars, flakes,
extrudates, but the composition is in the form of granules or tablets.
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When the composition comprises granules, the granules are preferably of a
particle size
of from I SO microns to 2500 microns, or even 1 S00 microns, or more
preferably 80% by
weight of the granules has an particle size of more than 300 microns (80% by
weight on
Tyler sieve mesh 48) and less than 10% by weight of the granules has a
particle size of
more than 1180 microns or even 710 microns (on Tyler mesh sieve24).
Preferably the detergent composition has a density of from 300g/litre to 1
SOOg/litre, or
more preferably from 400g/litre or even 580g/litre to 1200g/litre or even
850g/litre.
The detergent composition and the builder composition, as described above, may
comprise additional ingredients, preferred ingredients are described
hereinafter.
It has been found that detergent composition comprising as builder system or
part thereof
the builder component of the invention, preferably intimately mixed with any
of the
ingredients described herein, have an improved dispensing. Thus, the invention
also
provides a method for improving the dispensing of a detergent composition or
component thereof comprising a builder system, by providing a detergent
composition
comprising as builder system or part thereof a ground crystalline layered
silicate
whereof at least 90% or preferably at least 95% by weight has a particle size
of more than
20.2 microns and whereof at least 90% or preferably at least 95% by weight has
a
particle size of less than 100.2 microns.
Hereby is meant that the dispensing of the detergent composition or component
thereof
in the wash water, including from a dispensing drawer of a washing machine or
a
dispensing device, is improved compared to detergent compositions which
comprise do
not comprise the builder component of the invention. When used herein,
'improving the
dispensing' includes improving dissolution, reducing gelling and reducing
residue
formation.
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Additional ingredients
The builder component or 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 builder
component and the
compositions comprising the builder component and the precise nature of the
washing
operation for which it is to be used.
The builder component and the compositions herein preferably contain one or
more
additional detergent components selected from surfactants, bleaches, bleach
catalysts,
alkalinity systems, additional builders, organic polymeric compounds, enzymes,
suds
suppressors, lime soap, dispersants, soil suspension and anti-redeposition
agents soil
releasing agents, perfumes, brightners, photobleaching agents and additional
corrosion
inhibitors.
Surfactant
The builder component of the invention or the detergent compositions herein
preferably
contain one or more surfactants. The surfactant may comprise any surfactant
known in
the art selected from anionic, nonionic, cationic, ampholytic, amphoteric and
zwitterionic
surfactants and mixtures thereof.
It should be understood that for the purpose of the invention the detergent
composition
may comprise surfactant which is not present in the intimate mixture with the
crystalline
layered silicate, but present in the other detergent components.
Anionic Surfactant
The compositions and the builder component in accord with the present
invention
preferably comprise an anionic surfactant. Essentially any anionic surfactants
useful for
detersive purposes can be comprised in the detergent composition. 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,
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sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and
sulfonate
surfactants are preferred.
Highly preferred are surfactants systems comprising a sulfonate and a sulfate
surfactant,
preferably a linear or branched alkyl benzene sulfonate and alkyl
ethoxylsulfates, as
described herein, preferably combined with a cationic surfactants as described
herein.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 1 g
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
Anionic Sulfonate Surfactant
Highly preferred herein are anionic sulfonate surfactants. Particularly
suitable for use
herein include the salts of CS-C2p linear or branched alkylbenzene sulfonates,
but also
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. Most
preferred are
C9-C~4 linear alkyl benzene sulfonates.
Anionic Sulfate Surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, the CS-C 1 ~ acyl-N-(C 1-C4 alkyl)
and -N-(C 1-
C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the
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sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 10-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates and
the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C 1 p-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a
C 11-C 1 g, most preferably C 11-C 1 S alkyl sulfate which has been
ethoxylated with from
0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures
have been
disclosed in PCT Patent Application No. WO 93/18124.
Anionic Carboxvlate 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 C 1 g alkyl group, x is from 1 to 25, R 1 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
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or unsubstituted hydrocarbon having between l 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
(R 1 ) CH2 COOM, wherein R is a CS-C 1 ~ linear or branched alkyl or alkenyl
group, R 1
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.
Mid-chain branched anionic surfactants
Highly preferred herein, in particular for providing an improved surfactant
pertormance, are alkyl
chain, mid-chain branched surfactant compounds of the above formula wherein
the Ab
moiety is a branched primary alkyl moiety having the formula:
R Rl R2
CH3CHz(CH2)~"CH(CH2~CH(CH2h,CH(CH2)z-
wherein the total number of carbon atoms in the branched primary alkyl moiety
of this
formula (including the R, R1, and R2 branching) is from 13 to 19; R, R1, and
R2 are
each independently selected from hydrogen and C1-C3 alkyl (preferably methyl),
provided R, R l , and RZ are not all hydrogen and, when z is 0, at least R or
R 1 is not
hydrogen; 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 from 0 to 13; and w + x + y + z is from 7 to 13.
In general, for the mid-chain branched surfactant compounds of the surfactant
system,
certain points of branching (e.g., the location along the chain of the R, R1,
and/or R2
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PCT/US99/1531 I
moieties in the above formula) are preferred over other points of branching
along the
backbone of the surfactant. The formula below illustrates the mid-chain
branching range
(i.e., where points of branching occur), preferred mid-chain branching range,
and more
preferred mid-chain branching range for mono-methyl branched alkyl Ab moieties
useful
according to the present invention.
CH3CH2CHZCH2CH2CH2(CH2)~_~CHzCH2CH2CH2CH2-
more referred r
P ang~
preferred range
mid-chain branching ran
It should be noted that for the mono-methyl substituted surfactants these
ranges exclude
the two terminal carbon atoms of the chain and the carbon atom immediately
adjacent to
the -X - B group.
The formula below illustrates the mid-chain branching range, preferred mid-
chain
branching range, and more preferred mid-chain branching range for di-methyl
substituted
alkyl Ab moieties useful according to the present invention.
CH3CH2CH2CH2CH2CH2(CH2)o-6CH2CH2CHZCH2CH2
more referred ran
P g~
preferred range
mid-chain branching range
Preferred are surfactant compounds wherein in the above formula the Ab moiety
does not
have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly
attached to
one carbon atom).
The most preferred mid-chain branched surfactants compounds for use in the
detergent
compositions herein are mid-chain branched primary alkyl sulfonate and, even
more
preferably, sulfate surfactants. It should be understood that for the purpose
of the
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invention, it may be prefen ed that the surfactant system comprises a mixture
of two or
more mid-chain branched primary alkyl sulfate or sulphonate surfactants.
Preferred mid-chain branched primary alkyl sulfate surfactants are of the
formula
R R1 R2
CH3CH2(CH2)~H(CH2)xCH(CH2h,CH(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 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.
R, R1, and R2 are each independently selected from hydrogen and C1-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.
Examples of salt forming cations are lithium, sodium, potassium, calcium,
magnesium,
quaternary alkyl amines having the formula
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R3
R6-N -R4
RS
PCT/US99/15311
wherein R3, R4, RS and R6 are independently hydrogen, C 1-C22 alkylene, C4-C22
branched alkylene, C 1-C6 alkanol, C 1-C22 alkenylene, C4-C22 branched
alkenylene,
and mixtures thereof. Preferred cations are ammonium (R3, R4, R5 and R6 equal
hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and
mixtures
thereof. The monoalkanol ammonium compounds of the present invention have R3
equal to C1-C6 alkanol, R4, RS and R6 equal to hydrogen; dialkanol ammonium
compounds of the present invention have R3 and R4 equal to C 1-C6 alkanol, RS
and R6
equal to hydrogen; trialkanol ammonium compounds of the present invention have
R3,
R4 and RS equal to C 1-C6 alkanol, R6 equal to hydrogen. Preferred alkanol
ammonium
salts of the present invention are the mono-, di- and tri- quaternary ammonium
compounds having the formulas:
H3N+CH2CH20H, H2N+(CH2CH20H)2, HN+(CH2CH20H)3.
Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed
above; most
preferred is sodium.
Further regarding the above formula, 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 C 16
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.
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Another preferred surfactant system of the present invention have one or more
branched
primary alkyl sulfates having the formula
R1 R2
CH3CH2(CH2)xCH(CH2)yCH(CH2)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 11; 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.
Preferably, the surfactant system comprises at least 20% by weight of the
system, more
preferably at least 60% by weight , even more preferably at least 90% by
weight of the
system, of a mid chain branched primary alkyl sulfates, preferably having R1
and R2
independently hydrogen or methyl, provided R1 and R2 are not both hydrogen; x
+ y is
equal to 8, 9, or 10 and z is at least 2, whereby the average total number of
carbon atoms
in these sulfate surfactants is preferably from 15 to 17, more preferably from
16-17.
Furthermore, preferred surfactant systems are those, which comprise at least
about 20%,
more preferably at least 60%, even more preferably at least 905 by weight of
the system,
of one or more mid-chain branched alkyl sulfates having the formula:
CH3
(I) CH3 (CHZ)aCH (CHZ~CHz OS03M
or
CH3 CH3
(II) CHs (CH2)dCH (CH~e CHCH2 OS03M
or mixtures thereof; wherein M represents one or more cations; a, b, d, and a
are integers,
a+b is from 10 to 16, d+e is from 8 to 14 and wherein further
when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8;
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when a + b = I 1, a is an integer from 2 to 10 and b is an integer from 1 to
9;
when a + b = 12, a is an integer from 2 to I I and b is an integer from 1 to
10;
when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to
11;
when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to
12;
when a + b = 1 S, a is an integer from 2 to 14 and b is an integer from I to
13;
when a + b = I 6, a is an integer from 2 to 1 S and b is an integer from 1 to
I 4;
when d + a = 8, d is an integer from 2 to 7 and a is an integer from 1 to 6;
when d + a = 9, d is an integer from 2 to 8 and a is an integer from I to 7;
when d + a = 10, d is an integer from 2 to 9 and a is an integer from 1 to 8;
when d + a = 11, d is an integer from 2 to 10 and a is an integer from 1 to 9;
when d + a = 12, d is an integer from 2 to 11 and a is an integer from 1 to
10;
when d + a = I 3, d is an integer from 2 to 12 and a is an integer from 1 to 1
I;
when d + a = 14, d is an integer from 2 to 13 and a is an integer from 1 to
12;
whereby, when more than one of these sulfate surfactants is present in the
surfactant
system, the average total number of carbon atoms in the branched primary alkyl
moieties
having the above formulas 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, S-
methyl
pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol
sulfate, 8-
methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl
pentadecanol
sulfate, 1 I-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-
methyl
pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol
sulfate, S-
methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol
sulfate,
8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl
hexadecanol
sulfate, I I-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,S-
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17
methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl
tetradecanol
sulfate, 2,8-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
one branching unit are examples of preferred branched surfactants useful in
the present
invention compositions:
5-methylpentadecylsulfate having the formula:
~OS03M
CH3
6-methylpentadecylsulfate having the formula
H3
OS03M
7-methylpentadecylsulfate having the formula
OS03M
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.
PCT/US99/1531 I
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
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CH3 CH3
OS03M
2,9-dimethylpentadecylsulfate having the formula
CH3
OS03M
CH3
2,10-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
wherein M is preferably sodium.
Alkoxvlated Nonionic Surfactant
PC1'/US99/15311
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and
propoxylated nonionic surfactants are prefen:ed.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic
condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic
ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates
with propylene glycol, and the nonionic ethoxylate condensation products with
propylene
oxide/ethylene diamine adducts.
Nonionic Alkoxylated Alcohol Surfactant
Nonionic -surfactant can be present in the detergent compositions. It may be
preferred that
the level of ethoxylated nonionic surfactants in the intimate mixture are
below 10% by
weight of the mixture, preferably even 5% by weight.
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
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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 Polvhydroxv Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy
propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more
preferably
C1 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 17
alkyl or alkenyl, most preferably straight-chain C 11-C 17 alkyl or alkenyl,
or mixture
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at
least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably
ethoxylated or propoxylated) thereof. Z preferably will be derived from a
reducing sugar
in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic Fatty Acid Amide Surfactant
Suitable fatty acid amide surfactants include those having the formula:
R6CON(R7)2
wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17
carbon
atoms and each R7 is selected from the group consisting of hydrogen, C 1-C4
alkyl, C 1-
C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic Alkvlpolysaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from 6
to 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:
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R20(CnH2n0)t(glycosyl)x
PCT/US99/15311
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.
Amnhoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and
the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
from 0 to 5, preferably from 0 to 3; and each RS is an alkyl or hydroxyalkyl
group
containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3
ethylene
oxide groups. Preferred are C 10-C 1 g alkyl dimethylamine oxide, and C ~ 0_
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
compositions or the
builder 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
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PCT/US99/15311
phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants
are
exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R
is a C6-C 1 g hydrocarbyl group, each R 1 is typically C 1-C3 alkyl, and R2 is
a C 1-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.
Cationic Surfactants
Suitable cationic surfactants to be used 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 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,
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23
PCT/US99/15311
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:
R~ /ApRa
\N+ X_
R2~ ~R3
(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 -pI-I 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 R1
groups
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PCT/US99/15311
24
are linear alkyl groups. Linear RI 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\ /(CH2CH2O)2-5 H
/N
CH3/ \C H3
wherein R I is C 10-C I g hydrocarbyl and mixtures thereof, especially C 10-C
14 alkyl,
preferably C I 0 and C I 2 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 andJor Pr
and/or
i-Pr units.
The levels of the cationic mono-alkoxyIated 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:
__ R\ /A,pRs
\N+ X
~A,qRa
(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
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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 C 1-C4 alkoxy, especially ethoxy,
(i.e., -
CH2CH20-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30,
preferably
to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most
preferably both
p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
R' CH2CH20H
N+~ x0
CH3/ \CH2CH20H
wherein R 1 is C 1 p-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-
C14 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:
1
R~ +/(CH2CH20)pH
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 C1-C3 alkyl, preferably methyl, and X is
an anion,
especially chloride or bromide.
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PC'TNS99/15311
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.
Perhvdrate Bleaches
A preferred additional components of the builder component but preferably the
compositions herein is a perhydrate bleach, such as metal perborates, metal
percarbonates, particularly the sodium salts. Perborate can be mono or tetra
hydrated.
Sodium percarbonate has the formula corresponding to 2Na2C03.3H202, and is
available commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic
perhydrate
salt of use in the detergent compositions herein.
Organic Peroxvacid Bleaching_Svstem
A preferred feature of the composition or agglomerstes 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, such as the perborate bleach of the claimed invention. In an
alternative
preferred execution a preformed organic peroxyacid is incorporated directly
into the
.~omposition. Compositions containing mixtures of a hydrogen peroxide source
and
organic peroxyacid precursor in combination with a preformed organic
peroxyacid are
:also envisaged.
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Peroxvacid Bleach Precursor
PCT/US99/15311
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is
O
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of from
0.5% to 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 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.
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Preferred L groups are selected from the group consisting of
PCT/US99/15311
Y R3 R3Y
-O ~ , -O ~ Y , and -O
O
-N-C-.R~ O
-N N -N-C-CH-R4
R3 , ~ , ,
R3 Y
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
CH O Y
--C 4
O-C R~ N~C~NR4 , N.,~ /NR
O O
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 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+, -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
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PCfNS99/15311
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 Plkvl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R1--C,N-R2-CL R1-N-C~R2~C-L
i ~~ ! i~ i~
v
O R O or R5 O p
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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PCT/IJS99/15311
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 benzoyiating 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-acyl group-containing
perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine
and benzoyl
pyroglutamic acid.
Cationic Peroxvacid Precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part
of a suitable peroxyacid precursor compound with a positively charged
functional group,
such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl
ammonium group. Cationic peroxyacid precursors are typically present in the
solid
detergent compositions as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as
described
hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl
percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter.
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PCT/US99/15311
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594; EP
4?5,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of prefer ed cationic peroxyacid precursors are described in UK
Patent
Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650,
08/298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred
cationic
peroxyacid precursors of the N-acylated caprolactam class include the trialkyl
ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene
alkyl
caprolactams.
Benzoxazin Organic Peroxyacid Precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example
in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
O
II
I
N C-R1
wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed Oreanic Peroxyacid
The detergent composition may contain, in addition to, or as an alternative
to, an organic
peroxyacid bleach precursor compound, a preformed organic peroxyacid ,
typically at a
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PCTNS99/15311
level of from 1 % to 15% by weight, mare preferably from 1 % to 10% by weight
of the
composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
R 1 ____ C __.__ N ____ ._ R2 - C - OOH R 1 _- N _C __ ___ R2 _.__ C _. __.
OOH
O Rb O or R5 O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from I to 14 carbon atoms,
and RS is
H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide
substituted
organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid,diperoxytetradecanedioc acid and
diperoxyhexadecanedioc
acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach Catalyst
The builder component or the composition herein can contain a transition metal
containing bleach catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a
transition metal
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
catalysts are disclosed in U.S. Pat. 4,430,243.
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33
Other types of bleach catalysts include the manganese-based complexes
disclosed in U.S.
Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include
MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(CI04)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-(CI04)3, and mixtures thereof. Others are described in
European
patent application publication no. 549,272. Other ligands suitable for use
herein include
1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-
methyl-
1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and
mixtures
thereof.
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. 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
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wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each Rl-N=C-R2 and R3-C=N-R4 form a fve or six-membered ring.
Said ring can further be substituted. B is a bridging group selected from O,
S. CR5R6,
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.
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]-
(CI04)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 (ferric 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).
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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
concentration of 3-S fold may be required under U.S. conditions to achieve the
same
results.
Additional builder material
Water-Soluble Builders
The builder component or preferably compositions herein may contain a water-
soluble
builder compound, typically present in detergent compositions at a level of
from 1 % to
80% by weight, preferably from 10% to 60% by weight, most preferably from 15%
to
40% by weight of the composition.
The detergent compositions of the invention may comprise phosphate-containing
builder
material, preferably comprises tetrasodium pyrophosphate or even more
preferably
anhydrous sodium tripolyphosphate, present at a level of from 0.5% to 60%,
more
preferably from 5% to 50%, more preferably from 8% to 40. It may be preferred
that the
composiitons are free of phosphate-containing builder material.
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Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their
salts in which the polycarboxylic acid comprises at least two carboxylic
radicals
separated from each other by not more that two carbon atoms, borates, 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,
preferably present at a level of from 0.1 % to 1 S%, 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.
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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.
It may be preferred that the polymeric or oligomeric polycarboxylates are
present at
levels of less than 5%, preferably less than 3% or even less than 2% or even
0% by
weight of the compositions.
Borate builders, as well as builders containing borate-forming materials that
can produce
borate under detergent storage or wash conditions are useful water-soluble
builders
herein.
Insoluble Builder Compound
The builder component or the compositions herein may contain an insoluble
builder
compound, but preferably only present at a level of from 0% to 25% by weight,
most
preferably from 0% to 15% weight of the composition, or even 0% to 10% by
weight of
the composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. xH20
wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5
and x is at least
S, 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.
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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)86(Si02)106~. 276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder. Zeolite MAP
is
described in EP 384070A (Unilever). It is defined as an alkali metal alumino-
silicate of the zeoiite 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 d50 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 d5p value indicates that 50% by weight of the particles have a diameter
smaller than that figure. The particle size may, in particular be determined
by
conventional analytical 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.
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The builder component or the compositions herein may also comprise additional
silicate material, including amorphous silicate material, metaa-silicates,
additional
coarse crystalline layered silicate material of particle size of above 150
microns.
The additional silicate material is preferably present at a level of less than
20% by
weight of the compositions, preferably less than 15% by weight or even less
than
10% by weight.
Heavy metal ion sequestrant
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 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. i % 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, 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,
ethyienediamine
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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 described in EP-A-516,102 are also suitable herein.
The ~i-
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 ac,~d, 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.
E me
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.
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Preferred commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by
Gist-
Brocades, those sold by Genencor International, and those sold under the
tradename
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated
into
the compositions in accordance with the invention at a level of from 0.0001 %
to 4%
active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a special
strain of B
licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred
commercially
available amylases include for example, those sold under the tradename
Rapidase by
Gist-Brocades, and those sold under the tradename Termamyl, 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
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., Thermomyces sp. or Pseudomonas sp. including
Pseudomonas pseudoalcali enes or Pseudomas fluorescens. Lipase from chemically
or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is
derived from Pseudomonas pseudoalcali; enes, which is described in Granted
European
Patent, EP-B-0218272.
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Another preferred lipase herein is obtained by cloning the gene from Humicola
lams ig_nosa and expressing the gene in Asper illus oryza, as host, as
described in
European Patent Application, EP-A-0258 068, which is commercially available
from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This
lipase is
also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7,
1989.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the
compositions
herein or the agglomerates herein, where they may act such as to bind the
agglomerate
components together.
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 in accord
with the invention.
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.
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The polyamino compounds are useful herein including those derived from
aspartic acid
such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particulariy 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.
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 ~- OCH2CHZ)n N+ CH2 __ CH2 -(_ CH2)a N+ CH2CH20 )ri X
b
(CH2CH20 J~ X (CH2CH20 ~-ri X
wherein X is a nonionic group selected from the group consisting of H, CI-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 I or 0; for
cationic
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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~rstem
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 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
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.
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Other suitable antifoam compounds include the monocarboxylic fatty acids and
soluble
salts thereof. These materials are described in US Patent 2,954,347, issued
September
27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof,
for use
as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably 12 to 1$ 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-
alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products
of cyanuric
chloride with two or three moles of a primary or secondary amine containing 1
to 24
carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-
alkali metal
(e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75% to 95% by weight of the silicone antifoam
compound; and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by
weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from
5% to 50%, preferably 10% to 40% by weight;
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(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from I :0.9 to I:I.1, at a level of from 0.5% to 10%,
preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake
copolymer of this type is DC0544, commercially available from DOW Corning
under the tradename DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C I 6-C I 8
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to
I5, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731
and comprises a silicone antifoam compound and an organic 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, aluminosiiicate and
polycarboxylic
polymers, such as copolymers of laic and acrylic acid.
Polymeric Dve 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,
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polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers
can be
cross-linked polymers.
Optical Brightener
The compositions herein also optionally contain from about 0.005% to S% by
weight of
certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R~ R
N I~_H N
N N C C O N--CO N
~N H H N
R2 S03M S03M Rt
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming canon such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a canon
such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-
2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener
species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-
Geigy Corporation. Tinopal-CBS-X and Tinopal-IJNPA-GX is the preferred
hydrophilic
optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and
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.
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WO 00/02988 PCT/US99/1531 I
48
When in the above formula, Rl is anilino, R2 is morphilino and M is a cation
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species are
commercially
marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy
Corporation.
Polymeric Soil Release Agent
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.
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49
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 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
sulfoaroyl, 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
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 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
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METOLOSE SM200, which are the trade names 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
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. 4,525,5241'ung 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
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,
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 (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.
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51
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 or
tablet 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 gllitre or
even 350g/litre
or 420g/litre to 2000g/litre or more preferably to 1 SOOg/litre or 100 g/litre
or even to
700g/litre.
Laundry Washin;~ 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,
as are typical product dosages and wash solution volumes commonly employed in
conventional machine laundry methods.
The composition may also be formulated such that it is suitable for hard-
surface cleaning
or hand washing or for pre-treatment or soaking of soiled and stained fabrics.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
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LAS : Sodium 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 = C 12 - C
14
QAS I : R2.N+(CH3)2(C2H40I-I) with R2 = Cg - C11
SADS . Sodium C,4-C2, alkyl disulfate of formula
2-(R).C4 H,.-
1,4-(S04-)z where R = C,o_C,8
SADE2S : Sodium C,4-C,2 alkyl disulfate of formula
2-(R).C, H,.-
1,4-(S04-), where R = C,o-C,g, condensed
with z moles of
ethylene oxide
APA . Cg - C 10 amido propyl dimethyl amine
Soap . Sodium linear alkyl carboxylate derived
from an 80/20
mixture of tallow and coconut fatty acids
STS . Sodium toluene sulphonate
CFAA . C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA = C 16-C 18 alkyl N-methyl glucamide
TPKFA . C 16-C 18 toPPed whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP . Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12~2~H20 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
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53
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
200pm and 900~m
Bicarbonate Anhydrous sodium bicarbonate with a particle
: size
distribution between 400~m 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 dehydrate of activity
86.4% with a
particle size distribution between 425pm
and 850~m
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
weight about 10,000
AA . Sodium polyacrylate polymer of average molecular
weight 4,500
CMC : Sodium carboxymethyl cellulose
Cellulose etherMethyl 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
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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 (1) : Lipolytic enzyme, having 2.0% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Lipolase Ultra
Endolase : Endoglucanase enzyme, having 1.5% by
weight of active
enzyme, sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
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
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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.
PhotoactivatedSulfonated zinc phthlocyanine encapsulated
: in bleach (1)
dextrin soluble polymer
PhotoactivatedSulfonated alumino phthlocyanine encapsulated
. in bleach
(2) dextrin soluble polymer
Brightener Disodium 4,4'-bis(2-sulphostyryl)biphenyl
1 :
Brightener Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-
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)
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
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PVP : Polyvinylpyrolidone polymer, with an average
molecular
weight of 60,000
PVNO . Polyvinylpyridine N-oxide polymer, with an
average
molecular weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an average molecular weight of 20,000
QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-(C2H40))n, wherein n = from 20 to
30
S~RP 1 : Anionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short
block polymer
PEI : Polyethyleneimine with an average molecular
weight of
I $00 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: I to
100:1
Opacifier : Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron 621
Wax : Paraffin wax
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Examule 1
The following are detergent formulations according to the invention:
_ _ A B C D
Base Powder _ _
STPP - 10.0 -
Zeolite A 16.0 - - 16.0
C45AS 4.0 - 4.0 5.0
QAS I - 1.0 -
MBAS 17, 2.1 2.0 4.0 - -
C25 AE3S - 1.0 - 1.0
MA/AA 2.0 1.0 2.0 1.0
LAS 4.0 2.0 3.0 1.6
TAS - 4.0 - -
Silicate - 3.0 - 3.0
CMC 1.0 1.0 0.5 1.0
Brightener 2 0.2 0.2 - -
Soap 1.0 - - 1.0
DTPMP 0.4 0.4 0.2 0.4
Spray On
C45E7 - 2.5 - -
C25E3 2.5 - - -
Silicone antifoam 0.3 0.3 0.3 0.3
Perfume 0.3 0.3 0.3 0.3
Agglomerate
NaSKS-6 (II) 9.0 16.0 10.0 6.8
LAS 8.0 9.0 4.0 S.0
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Dry additives
QEA - 0.5 1.0 -
Carbonate 6.0 13.0 15.0 13.0
PB4 18.0 18.0 10.0 -
PB 1 4.0 4.0 - -
NOBS 3.0 4.2 1.0 -
Photoactivated bleach 0.02 0.02 0.02 0.02
Manganese catalyst - - 0.5 -
Protease 1.0 1.0 1.0 1.0
Lipase 0.4 0.4 0.4 0.4
Amylase 0.25 0.30 0.15 0.3
Dry mixed sodium sulfate3.0 3.0 5.0 3.0
Balance (Moisture & 100.0 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670 670
Example 2
The following are detergent formulations according to the present invention:
E F G H
Base product:
TAS - 1.0 4.0 -
LAS 5.0 - 11.0 8.0
C45AS 4.0 4.0 6.0 6.0
MES 3.0 -
QAS II 0.4 - 1.0 -
TFAA - 1.0 - __ _.
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59
C25E5/C45E7/CZ- 2.0 - I.0
sE3
- 18.0 - -
Zeolite 9.0 5.0 - 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5 - -
DTPMP 0.7 1.0 - -
SRP I 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.2 5
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 - -
Photoactivated70ppm 45ppm - 1 Uppm
bleach (ppm)
Brightener 0.2 0.2 0.08 0.2
1
PB 1 6.0 2.0 - -
NACA - - - 3.0
NAC OB S 2.0 1.0 0.9 3.1
Agglomerate:
NaSKS-6 (I) 6.6 6.0 20.0 10.0
LAS 3.0 - 15.0 7.0
C45 AS 3.0 6.0 - -
Balance (Moisture100 100 100 100
and
Miscellaneous)
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Example 3
The following are detergent formulations according to the present invention:
I J K
Base Powder
MBAS 17.5, 1.8 - - 2.0
Zeolite A - 22.0 6.0
Sodium sulfate 1.0 5.0 -
MA/AA 3.0 3.0 3.0
MES - 5.0 -
LAS - - 3.5
C45AS 3.0 4.0 7.0
Silicate - 1.0 5.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 5.0
Citric acid 3.0 2.0 1.5
Spray On
C45E5 1.0 1.0 -
Agglomerate
NaSKS-6(I) or(II) 17.0 6.0 7.0
LAS/MES 10.0 6.0 5.0
Moisture 0.5 0.1 0.5
Dusted Zeolite - 0.8 0.5
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
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Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS - 6.1 -
NAC OBS - - 4.5
Sodium sulfate - 6.0 -
Balance (Moisture 100 100 100
and
Miscellaneous)
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Example 4
The following are high density and bleach-containing detergent formulations
according
to the present invention:
L M N
Blown Powder
Zeolite A - - 1 S.0
Sodium sulfate 0.0 5.0 0.0
LAS 3.0 - 3.0
C45AS 3.0 2.0 4.0
QAS - - 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
QAS 1.0 - -
LAS - 11.0 7.0
TAS 2.0 2.0 1.0
Silicate 3.0 - 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Agglomerate
NaSKS-6 (I) or (II) 15.0 12.0 5.0
LAS 8.0 7.0 4.0
AS S.0 - -
Spray On
Encapsulated Perfume 0.3 0.3 0.3
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C25E3 2.0 - 2.0
Dry additives
QEA 1.0 0.~ 0.5
Citric/Citrate S.0 - 2.0
Bicarbonate - 3.0 -
Carbonate 8.0 1 ~.0 10.0
NAC OBS 6.0 - 5.0
Manganese catalyst - - 0.3
NOBS - 2.0 -
PB 1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Citric acid - - 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
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Example 5
The following are high density detergent formulations according to the present
invention:
O P Q R
Agglomerate
QAS 2.0 - 2.0 -
MES - 2.0 - -
LAS 6.0 - - -
TAS - 2.0 - -
C45AS 6.0 4.0 2.0 -
MBAS 16.5, 1.9 4.0 - - -
Zeolite A 15.0 6.0 - -
Carbonate 4.0 8.0 4.0 8.0
MA/AA 4.0 2.0 - 2.0
CMC 0.5 0.5 - 0.5
DTPMP 0.4 0.4 - 0.5
Spray On
C25E3 1.0 1.0 - -
Perfume 0.5 0.5 0.5 0.5
Agglomerate
SKS-6 7.0 15.0 20.0 10.0
LAS 5.8 9.0 15.0 10.0
Zeolite - 0.9 - -
C45 AS - 3.0 - -
Water 0.08 0.1 - 0.2
Dry Adds
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EDDS/HEDP 0.5 0.3 0.5 0.8
NaSKS 6 (I) 5.0 6.0 4.0 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 15.0 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
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Example 6
S T U V W X
C45AS 11.0 S.0 4.6 6.5 4.1 9.0
C25AES 1.3 1.0 - 1.3 1.0 -
LAS - 3.0 2.7 - 2.0 -
C25E3/ C25E5 1.5 4.7 3.3 - 4.7 3.3
MBAS 16.5, 1.7 15.0 12.0 10.0 10.2 7.0 14.1
QAS - 1.15 0.6 - 1.7 -
Zeolite A 5.0 16.7 - 7.0 16.7 11.2
SKS-6/LAS agglomerate 20.0 - 17.5 20.0 9.0 17.5
5:4
Citric acid - 1.5 2.5 - 1.5
MA/AA - 0.6 - - 0.6
MA/AA 3 - - 7.03 - _ _ 7.03
_
_
AA 2.3 - - 2.8 - -
EDDS - 0.3 - - 0.3 -
HEDP - 0.5 - - 0.5 -
Carbonate 6.0 12.5 14.5 6.0 12.5 14.0
Silicate 0.58 0.8 12 0.58 0.8 12
PB 1 11.0 - 14.0 - - 4.0
NACA-OBS - 4.7 - - 2.7
PC - 17.3 - 20.0 17.3 -
NOBS - - 4.0 - - 4.0
TAED - 2.5 - - 3.5 2.0
Protease 0.25 0.36 0.2 0.26 0.36 0.2
Lipase _ _ _ - - __ _
_.
Cellulase 0.3 0.26 - 0.3 0.26
Amylase - 0.36 - - 0.36 -
Brightener 0.17 0.06 0.30 0.17 0.06 0.30
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SRP1 0.4 0.2 0.~ 0.4 0.2 0.~
PEG 1.6 - 0.19 1.6 - 0.19
Sulfate 5.5 6.4 3.5 5.5 6.4 3.5
CMC - 0.5 - - 0.5 _ _
_
-
MgS04 - 0.13 - - 0.13 -
Photobleach - 0.0026- - 0.0026-
Silicone anti-foam 0.02 0.21 0.17 0.02 0.21 0.17
Perfume 0.42 0.55 0.25 0.42 0.55 0.25
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Example 7
The following laundry detergent compositions Y to AB are prepared in accord
with the
invention:
Y Z AA AB
MBAS 16.5, 1.7 - - - 5.5
C45 AS 9.0 8.0 4.1 4
C45E1 S 1.0 - - -
LAS - - 3.7
C 16 SAS - 2.0 - -
MES - - _. 4
C23E6.5 - 1.5 - 1.5
SKS-6/LAS agglomerate18.0 10.0 35.0 12.0
5:4
Zeolite A 7.8 17.0 - 20.0
AA 2.3 2.3 2.3 2.3
Carbonate 7.0 7.0 12.5 2.5
Silicate 0.6 0.6 0.6 -
Perborate/PC 11.0 2.0 - -
Protease 0.3 0.3 0.3 0.3
Cellulase 0.3 0.3 0.3 0.3
SRP1 0.4 0.4 0.4 0.4
Brightener 0.2 0.2 0.2 0.2
PEG 1.6 1.6 1.6 1.6
Sulfate 5.5 5.5 5.5 5.5
Silicone Antifoam 0.42 0.42 0.42 0.42
Moisture & Minors ---Balance---
Density (g/L) 663 663 663 663
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Example 8
The following laundry detergent compositions AC to AG are prepared in accord
with the
invention:
AC AD AE AF AG
MBAS 16.5, 1.7 14.8 16.4 12.3 8.2 4.1
C45 AS 6.0 8.0 4.3 4.0 S.0
C45E1S 2.0 - - 1.0 -
LAS - - - 3.0 5.0
C16 SAS - 1.0 - - -
MES - 5.0 - - -
TFAA 1.6 0 0 0 0
C24E3 4.9 4.9 4.9 4.9 4.9
Zeolite A S.0 15 - - -
NaSKS-6lLAS 3:2-21 7 22 17 20
spray-dried particle
Citrate/citric 1.0 3 3 2.0 -
MA/AA 4.8 4.8 4.8 4.8 4.8
HEDP 0.5 0.5 0.5 0.5 0.5
Carbonate 8.5 8.5 8.5 8.5 8.5
Percarbonate 20.7 20.7 20.7 20.7 20.7
TAED 4.8 4.8 - - 4.8
NACA-OBS - - 5.0 6.0 2.0
Protease 0.9 0.9 0.9 0.9 0.9
Lipase 0.15 0.15 0.15 0.15 0.1
S
Cellulase 0.26 0.26 0.26 0.26 0.26
Amylase 0.36 0.36 0.36 0.36 0.36
S1ZP1 0.2 0.2 0.2 0.2 0.2
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Brightener 0.2 0.2 0.2 0.2 0.2
Sulfate 2.3 2.3 2.3 2.3 2.3
QEA 1.0 1.0 - - -
QAS 1.0 - - - 1.0
Silicone Antifoam0.4 0.4 0.4 0.4 0.4
Moisture & Minors---Balance---
Density (g/L) 850 850 850 850
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Example 9
The following formulations are examples of compositions in accordance with the
invention, which may be in the form of granules or in the form of a tablet.
AH ~ AI AJ AK AL
Base Product
C45 AS/TAS 8.0 5.0 3.0 3.0 3.0
LAS 8.0 - 8.0 - 7.0
C25AE3S 0.5 2.0 1.0 - -
LAS/NaSKS-6 (I) or 5.0 17.0 9.0 20.0 15.0
(II)
Agglomerate at ratio
3:2
C25AE5/AE3 2.0 - 5.0 2.0 2.0
QAS - - - 1.0 1.0
Zeolite A 20.0 10.0 10.0 - 10.0
SKS-6 (I) (dry add) - - 2.0 - -
MA/AA 2.0 2.0 2.0 - -
AA - - - - 4.0
Citrate - 2.0 - - -
Citric acid 2.0 - 1.5 2.0 -
DTPA 0.2 0.2 - - -
EDDS - - 0.5 0.1 -
HEDP - - 0.2 0.1 -
PB1 3.0 5.0 10.0 - 4.0
PC - - - 18.0 -
NOBS 3.0 4.0 - - 4.0
NACA OBS - - 2.0 - -
TAED - - 2.0 5.0 -
Carbonate 15.0 18.0 8.0 15.0 15.0
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Sulphate 5.0 12.0 2.0 17.0 3.0
Silicate - 1.0 - - 8.0
Enzyme 0.3 0.3 1.0 1.0 0.2
Minors (Brightener/SRP1/0.5 0.5 0.5 0.5 0.5
CMC/Photobleach/ MgS04/
PVPVI/Suds suppressor/
PEG)
Perfume 0.2 0.3 0.5 0:2 0.1
