Note: Descriptions are shown in the official language in which they were submitted.
CA 02345581 2001-03-27
w wo oonosa6 Pc~rn~s9smo2o
i
FOAMING SYSTEM AND DETERGENT COMPOSITIONS
CONTAINING THE SAME
FIELD
~o This invention relates to a novel foaming system useful in a detergent
composition. More particularly, the present invention relates to granular
detergent compositions intended for cleaning fabrics containing novel foaming
components.
BACKGROUND
is Foam or suds formation is desired in various applications, such as during
the wash process. In detergent compositions, specific surfactants are known to
provide sudsing in the wash water. Not only is the formation of foaming or
sudsing desirable, but there is also a desire to readily create foam as well
as
maintaining the foam for a desired duration. For example, it may be desired
that
2o the foam occurs immediately upon contact of a detergent composition with
water.
Although there are various reasons as to why foam formation is desired, one
known reason is that consumers who use detergent compositions directly
associate the formation of foam with the cleaning ability of the detergent
composition.
2s Although the formation of foam is desired, foam may also pose problems
during the washing process. For example, drainage of the suds or foam during
the washing process may be difficult. Particularly for a machine wash process,
the suds or foam may hamper the drainage of the wash solution from the
machine before the rinse stage. Therefore, it is desired to gradually suppress
3o the formation of foam over time.
Accordingly, there is a need to produce foaming or sudsing early in the
wash process, such as when the detergent composition first comes into contact
with water, as well as a foam suppressing component to control the foam after
formation.
CA 02345581 2004-04-20
2
None of the existing art provides all of the advantages and benefits of the
present invention.
SUMMARY
This need is met by the present invention which is directed to a controlled
s foaming system especially adapted for use in detergent compositions
containing
a foaming component capable of providing foaming or sudsing without agitation,
and a delayed-release foam suppressing component. The present invention also
relates to detergent compositions containing the controlled foaming system.
These and other features, aspects, and advantages of the present
invention will become evident to those skilled in the art from a reading of
the
present disclosure and the appended claims.
DETAILED DESCRIPTION
While this specification concludes with claims distinctly pointing out and
particularly claiming that which is regarded as the invention, it is believed
that the
~s invention can be better understood through a careful reading of the
following
detailed description of the invention. In this specification, all percentages,
ratios,
and proportions are by weight, all temperatures are expressed in degrees
Celsius, molecular weights are in weight average, and the decimal is
represented
by the point (.), unless otherwise indicated.
zo
As used herein, "comprising" means that other steps and other ingredients
which do not affect the end result can be added. This term encompasses the
terms "consisting of and "consisting essentially of'.
is As used herein, the term "alkyl" means a hydrocarbyl moiety which is
straight or branched, saturated or unsaturated. Unless otherwise specified,
alkyl
moieties are preferably saturated or unsaturated with double bonds, preferably
with one or two double bonds. Included in the term "alkyl" is the alkyl
portion of
acyl groups.
so The present invention is directed to a controlled foaming system
especially adapted for use in detergent compositions containing a foaming
component capable of providing foaming or sudsing without agitation, and a
delayed-release foam suppressing component. Preferably, the delayed-release
foam suppressing component is a silicone foam suppressing agent which is
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3
releasably incorporated in a carrier, thereby delaying the release of the
silicone
foam suppressing agent.
When the controlled foaming system first comes into contact with water,
the foaming component generates rapid and stable foaming without agitation.
s When used herein, the term Gfoaming" means any form of formation of gas
bubbles, including sudsing and effervescing. Agitation is not necessary, but
may
enhance the generation of foam, and thus, may be preferred. Preferably, the
foaming component produces upon contact with water, gas bubbles having an
average bubble particle size of about 400 microns or less, preferably about
200
~o microns or less, and more preferably about 100 microns or less.
After the formation of foam, the delayed-release foam suppressing
component is released over time and the foaming is suppressed or otherwise
controlled by decreasing the amount of foam. Depending on when the foam
should be suppressed, the time delay may be adjusted by choosing the
is appropriate type of foam suppressing component. For example, for some
machine wash conditions, the foam suppressing component reduces the water
gas bubbles as early as upon agitation, so that preferably after about 120
seconds, the bubbles have been reduced at least about 30%. Also for example
in some other machine wash conditions, after from about 360 seconds to about
20 600 seconds, the bubbles have been reduced to from about 40 to about 70%
percentage, or otherwise become substantially suppressed before the rinse
stage.
Preferably for hand wash conditions, the foam suppressing component
may not reduce the water gas bubbles at the initial stages in the wash, since
it
2s may be preferable to maintain the amount of foam for a longer period of
time.
In one preferred embodiment, the foaming component and the delayed-
release foam suppressing component are independent dry particles. The term
"dry" is to be understood that the particles of the raw materials are
substantially
free of water, i.e., that no water has been added other than the moisture of
the
3o raw materials themselves. Typically, the level of water is below about 5%
by
weight of the total particle, preferably below about 3% and more preferably
below
about 1.5%.
For example in a detergent composition, such as a granular detergent
composition, the final composition contains a mixture of the two types of
particles
3s in addition to other conventional detersive components. In another
preferred
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4
embodiment one of the particles is present as a part of an other conventional
detersive component. Having separate particles is particularly useful because
one can control the different levels and thus provide controlled delivery of
the
foaming component and the suppressing component to the washing process,
s e.g., both a more efficient and a time delivery can be achieved, to provide
optimum performance.
Although not wanting to be limited by theory, it is believed that a detergent
composition having a controlled foaming system, especially in the early phases
of the wash cycle, has cleaning benefits. For example, it is believed that the
to foam helps transfer the surfactant in the detergent composition onto the
soil to
be removed and/or on to the fabric. In addition, it is believed that the foam
helps
further wetting and dissolution of the detergent composition. Furthermore, the
foam is believed to provide an early reservoir of unprecipitated surfactant to
wet
fabrics and helps suspend the soil in the wash solution.
is The controlled foaming system also is storage stable. For example, the
components do not degrade during storage while being exposed to moisture
from the air. In addition, because the foaming component contains an
effervescent granule, the incorporation of the controlled foaming system in a
detergent composition improves the dissolution characteristics of the active
2o ingredients present in the detergent composition.
Another advantage of the present invention is the improved dispensing
characteristics associated to the detergent compositions of the present
invention,
e.g., the detergent compositions intended for use in a drum-type fabric
washing
machine. Indeed, a difficulty with conventional high density granular
detergent
2s compositions is that they are not easily flushed from the dispenser drawer
of a
washing machine: i.e. when the granular composition is wetted by the water
flowing through the dispenser, the detergent ingredients may become stuck
together resulting in considerable residues of wetted and adhering powder left
behind the drawer. Similar problems are encountered when using such granular
3o detergent compositions in a dosing device in the washing drum. The presence
of
the effervescent granule in the granular detergent compositions provides
improved dispensing typically when used in a washing machine and good
storage stability in respect of the dispensing potential.
The detergent compositions containing the controlled foaming system are
3s preferably solid laundry or dish washing compositions, preferably in the
form of
CA 02345581 2004-04-20
granules, extrudates, or tablets. Preferably, granular detergent compositions
have a density of at least about 500 gll, more preferably at least about 700
gll.
The detergent compositions as well as the foaming component and the delayed-
release foam suppressing component may also comprise additional ingredients,
as described herein. The precise nature of these additional ingredients, and
levels of incorporation thereof will depend on the application of the
component or
composition and the physical form of the component and composition.
A. Foaming Component .
The foaming component preferably contains an effervescent granule. Any
~o effervescent granule capable of forming gas upon contact with water, known
in
the art, can be used. A preferred effervescent granule comprises an acid
source, capable of reacting with an alkali source in the presence of water to
produce a gas.
The acid source may be any organic, mineral or inorganic acid, or a
~s derivative thereof, or a mixture thereof. Preferably the acid source
comprises an
organic acid. The acid source is preferably substantially anhydrous or non-
hydroscopic and the acid is preferably water-soluble. It may be preferred that
the
acid source is overdried. Suitable acids source components include an acid or
salt form of a mono or polycarboxylic acid. Such preferred acids include those
Zo selected from the group consisting of citric, malic, maieic, fumaric,
aspartic,
glutaric, tartaric, malonic, succinic or adipic acid, monosodium phosphate,
boric
acid, 3 chetoglutaric acid, citramalic acid, and mixtures thereof. Citric
acid, malefic
or malic acid are especially preferred.
Also preferably, the acid source provides acidic compounds which have
zs an average particle size in the range of from about 75 microns to about
1180
microns, more preferably from about 150 microns to about 710 microns,
calculated by sieving a sample of the source of acidity on a series of
TylerT""
sieves.
The effervescent granule preferably comprises an alkali source. Any alkali
3o source which has the capacity to react with the acid source to produce a
gas may
be present in the particle, including sources capable of producing nitrogen,
oxygen or carbon dioxide gas. Preferred can be perhydrate bleaches and
silicate
material. The alkali source is preferably substantially anhydrous or non-
hydroscopic. !t may be preferred that the alkali source is overdried.
CA 02345581 2004-04-20
6
Preferably the produced gas is carbon dioxide, and therefore the alkali
source is preferably a source of carbonate; and in particular, a carbonate
salt.
Examples of preferred carbonates are the alkaline earth and alkali metal
carbonates, including sodium or potassium carbonate, bicarbonate and sesqui-
carbonate and any mixtures thereof with ultra-fine calcium carbonate such as
are
disclosed in German Patent Application No. 2,321,001 published on November
15, 1973. Alkali metal percarbonate salts are also suitable sources of
carbonate
species, which may be present combined with one or more other carbonate
sources.
to The carbonate and bicarbonate preferably have an amorphous structure.
The carbonate and/ or bicarbonates may be coated with coating materials. The
particles of carbonate and bicarbonate can have a mean particle size of about
75 microns or greater, preferably about 150pm or greater, more preferably of
about 250pm or greater, preferably about 500~m or greater. It may be preferred
~s that the carbonate salt is such that fewer than about 20% (by weight) of
the
particles have a particle size below about 500p.m, calculated by sieving a
sample
of the carbonate or bicarbonate on a series of Tyler sieves. Alternatively or
in
addition to the previous carbonate salt, it may be preferred that the fewer
than
60% or even 25% of the particles have a particle size below 150pm, whilst
fewer
2o than 5% has a particle size of more than 1.18 mm, more preferably fewer
than
20% have a particle size of more than 212 Vim, calculated by sieving a sample
of
the carbonate or bicarbonate on a series of Tyler sieves.
The molecular ratio of the acid source to the alkali source present in the
particle core is preferably from about 60;1 to about 1:60, more preferably
from
2s about 20:1 to about 1:20, more preferably from about 10:1 to about 1:10,
more
preferably from about 5:1 to about 1:3, more preferably from about 3:1 to
about
9:2, more preferably from about 2:1 to about 1:2.
In a preferred embodiment, the effervescent granule optionally contains a
binder which binds the acid source with the alkali source. Preferably, the
3o effervescent granule comprises up to about 50 % by weight of the total
granule of
a binder or a mixture thereof, preferably up to about 35% and more preferably
up
to about 20%. Suitable binders to use herein are those known to those skilled
in
the art and include anionic surfactants like C6-C20 alkyl or alkyiaryl
sulphonates
or sulphates, preferably C8-C20 alkylbenzene sulphonates, cellulose
derivatives
3s such as carboxymethylcellulose and homo- or co- polymeric polycarboxyiic
acid
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7
or their salts, nonionic surfactants, preferably C10-C20 alcohol ethoxylates
containing from 5-100 moles of ethylene oxide per mole of alcohol and more
preferably the C15-C20 primary alcohol ethoxylates containing from 20-100
moles of ethylene oxide per mole of alcohol. Of these tallow alcohol
ethoxylated
s with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of
ethylene oxide per mole of alcohol (TAE50) are preferred. Other preferred
binders include the polymeric materials like polyvinylpyrrolidones with an
average
molecular weight of from 12 000 to 700 000 and polyethylene glycols with an
average weight of from 600 to 10 000. Copolymers of malefic anhydride with
~o ethylene, methylvinyl ether, methacrylic acid or acrylic acid are other
examples of
polymeric binders. Others binders further include C10-C20 mono and diglycerol
ethers as well as C10-C20 fatty acids. In the embodiment of the present
invention where a binder is desired C8-C20 alkylbenzene sulphonates are
particularly preferred.
is In another preferred embodiment, the foaming component may also
contain a surface active component which reduces the water air surface
tension.
The preferred surface active component has a melting point above 45°C,
and is
preferably selected from the group consisting of nonionic alkoxylated amides,
alkyl esters of fatty acids, or alkoxylated alcohols. Especially preferred
surface
2o active components are selected from the group consisting of polyhydroxy
fatty
acid amides and condensation products of aliphatic alcohols with from about 1
to
about 15 moles of alkylene oxide. If a surface active component is used, the
weight ratio of the surface active component to the effervescent granule is
preferably from about 20:1 to about 1:10.
2s In still another preferred embodiment, the foaming component may further
include the addition of suds boosters. The suds boosters may enhance the
formation of suds in conjunction with the effervescent granule. The suds
booster
may be part of the same particle or component as the foaming component, or the
suds booster may be a separate independent particle or component.
3o Preferred suds boosters include amine oxide, polyethylene glycol,
monoethanol amine, diethanol amine, fatty alcohol, sugar, protein, betaine,
and
mixtures thereof.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
ss acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing
from 8
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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 R5 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
s are C10-C1g alkyl dimethylamine oxide, and C10-18 acylamido alkyl
dimethylamine oxide.
Suitable betaines are those compounds having the formula
R(R')2N+R2C00- wherein R is a Cg-C1g hydrocarbyl group, each R1 is typically
C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are C12_
~0 1g dimethyl-ammonio hexanoate and the C10-18 acylamidopropane (or ethane}
dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable
for
use herein.
The foaming component may be made my conventional methods,
including as part of a tabletting process, extrusion process, and/or an
is agglomeration process. The foaming component, whether in the form of a
particle or comprised in a particle, is preferably such that about 80% by
weight of
the particles have a particle size of more than 75 microns (more than 80% by
weight of the particles on Tyler sieve mesh 200) and less than about 10% by
weight of the particles have a particle size of more than 2 cm; preferably 80%
by
2o weight of the particles have a particle size of more than about 150 microns
(80%
by weight on Tyler sieve mesh 100) and less than about 10% by weight of the
particles have a particle size of more than about 1 cm; or more preferably 80%
by weight of the particles have a particle size of more than about 300 microns
(80% by weight on Tyler sieve mesh 48) and less than about 10% by weight of
2s the particles have a particle size of more than about 0.5 cm; or even more
preferably the particles have an average particle size of from about 500
microns
(on Tyler sieve mesh 32) to about 3000 microns, more preferably from about 710
microns (on Tyler mesh sieve 24) to about 1180 microns (through Tyler mesh
sieve 14).
3o B. Delayed-release Foam Suppressing Component
A suds suppressing amount of the delayed-release foam suppressing
component is used in the present invention. The term "delayed-release foam
suppressing component" means that the foam suppressing component begins to
suppress foam over time. Depending on when the foam should be suppressed,
ss the time delay may be adjusted by choosing the appropriate type of foam
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suppressing component. The term "suds suppressing amount" is meant that the
formulator of the detergent composition selected an amount of this component
which will control the suds to the extent desired. The amount of suppressing
component will vary with the detergent component selected.
A preferred delayed-release foam suppressing component is a silicone
foam suppressing component. One preferred silicone foam suppressing
component contains a silicone suds controlling agent having an average droplet
diameter of from 1 to 50 microns, releasably incorporated in a water-soluble
or
water dispersible, substantially non-surface active, detergent-impermeable,
and
io non-hydroscopic carrier, the silicone foam suppressing component being
substantially free of water-soluble relatively hydroscopic inorganic salts and
in
the form of an irregularly shaped particle having a minimum dimension of not
less
than about 0.05 cm and the maximum dimension being at least about 20%
greater than the minimum dimension.
is The preferred suppressing component contains a silicone suds controlling
agent which is substantially isolated from the other detersive components of
the
detergent composition. This "isolation" is achieved by incorporating the
controlling agent in a water-soluble or water-dispersible organic carrier
matrix.
The matrix is preferably a substantially non-surface active, non-hydroscopic
2o material which does not interact with the controlling agent. Moreover, the
carrier
must be substantially impenetrable by the detersive components to prevent
undesirable silicone/detergent and/or silicone/alkalinity interactions.
Moreover
the carrier matrix herein preferably does not contain added surface active
agents,
other than the silicone. The carrier is selected such that, upon admixture
with
2s water, the carrier matrix dissolves or disperses to release the silicone
suds
controlling agent to perform its suds or foam controlling function.
The silicone materials employed as the preferred silicone suds controlling
agents herein can be alkylated polysiloxane materials of several types, either
singly or in combination with various solid materials such as silica aerogels
and
3o xerogels and hydrophobic silicas of various types. in industrial practice,
the term
"silicone" has become a generic term which encompasses a variety of relatively
high molecular weight polymers containing siloxane units and hydrocarbyl
groups
of various types. In general terms, the silicone suds controllers can be
described
as siloxanes having the general structure backbone.
CA 02345581 2004-04-20
R
-(
I
R'
wherein x is from 20 to 2,000 and R and R' are each alkyl or aryl groups,
especially methyl, ethyl, propyl, butyl or phenyl. The poiydimethylsiioxanes
(R
and R' are methyl) having a molecular weight within the range of from 200 to
s 200,000, and higher, are all useful as suds controlling agents. Silicone
materials
are commercially available from the Dow Corning Corporation under the trade
mark Silicone 200 Fluids. Suitable polydimethylsiloxanes have a viscosity of
from 2x10'5 to 1.5x10-3 m2s-'(20-1500cs), at 25°C when used with silica
and/or
siloxane resin.
io Additionally, other silicone materials wherein the side chain groups R and
R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful
suds
controlling properties. These materials are readily prepared by the hydrolysis
of
the appropriate alkyl, aryl or mixed alkylaryl or aralkyl silicone dichlorides
with
water in the manner well known in the art. As specific examples of such
silicone
i s suds controlling agents useful herein there can be mentioned, for example,
diethyl polysiloxanes; dipropyl polysiloxanes; dibutyl polysiloxanes;
methylethyl
polysiloxanes; phenylmethyl polysiloxanes; and the like. The dimethyl
polysiioxanes are particularly useful herein due to their low cost and ready
availability.
?o The silicone "droplets" in the carrier matrix preferably have an average
diameter of about 1 to about 50 pm, preferably from about 5 to about 40 pm,
more preferably from about 5 to about 30 pm for maximum effectiveness.
Droplets below about 5 pm in diameter are not very effective and above about
30
~m in diameter are increasingly less effective. Similar sizes are required for
the
zs other silicone suds controlling agents disclosed hereinafter.
A second highly preferred type of silicone suds controlling agent useful
herein comprises a mixture of an alkylated siloxane of the type hereinabove
disclosed and solid silica. Such mixtures of silicone and silica can be
prepared by
affixing the silicone to the surface of silica (Si02), for example by means of
the
3o catalytic reaction disclosed in U.S. Pat. No. 3,235,509. Suds controlling
agents
comprising mixtures of silicone and silica prepared in this manner preferably
comprise silicone and silica in a silicone:silica ratio of from 19:1 to 1:2,
preferably
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11
from 10:1 to 1:1. The silica can be chemically and/or physically bound to the
silicone in an amount which is preferably 5% to 20%, preferably from 10 to
15%,
by weight, based on the silicone. The particle size of the silica employed in
such
silica/silicone suds controlling agents should preferably be not more than
about
s 1000, preferably not more than 100 nm, preferably from 5 nm to about 50 nm,
more preferably from 10 to 20 nm, and the specific surface area of the silica
should exceed about 5 m2/g., preferably more than about 50 mz/g.
Alternatively, suds controlling agents containing silicone and silica can
be prepared by admixing a silicone fluid of the type hereinabove disclosed
with a
~o hydrophobic silica having a particle size and surface area in the range
disclosed
above. Any of several known methods may be used for making a hydrophobic
silica which can be employed herein in combination with a silicone as the suds
controlling agent. For example, a fumed silica can be reacted with a trialkyl
chlorosilane (i.e., "silanated") to affix hydrophobic trialkylsilane groups on
the
is surface of the silica. In a preferred and well known process, fumed silica
is
contacted with trimethylchlorosilane and a preferred hydrophobic silanated
silica
useful in the present compositions is prepared.
In an alternate procedure, a hydrophobic silica useful in the present
compositions is obtained by contacting silica with any of the following
2a compounds: metal, ammonium and substituted ammonium salts of long chain
fatty acids, such as sodium stearate, aluminum stearate, and the like;
silylhalides, such as ethyltrichlorosilane, butyltrichlorosilane,
tricyclohexylchlorosilane, and the like; and long chain alkyl amines or
ammonium
salts, such as cetyl trimethyl amine, cetyl trimethyl ammonium
2s chloride, and the like.
A preferred suds controlling agent herein comprises a hydrophobic
silanated (most preferably trimethylsilanated) silica having a particle size
in the
range from about 10 nm to about 20 nm and a specific surface area above about
50 m2 Ig intimately admixed with a dimethyl silicone fluid having a molecular
so weight in the range of from 500 to 200,000, at a weight ratio of silicone
to
silanated silica of from 10:1 to 1:2. Such suds controlling agents preferably
comprise silicone and the silanated silica in a weight ratio of
siliconeailanated
silica of from 10:1 to 1:1. The mixed hydrophobic silanated (especially
trimethylsilanated) silica-silicone suds controlling agents provide suds
control
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12
over a broad range of temperatures, presumably due to the controlled release
of
the silicone from the surface of the silanated silica.
Another type of suds control agent herein comprises a silicone material
of the type hereinabove disclosed sorbed onto and into a solid. Such suds
s controlling agents comprise the silicone and solid in a siliconeaolid ratio
of from
20:1 to 1:20, preferably from 5:1 to 1:1. Examples of suitable solid sorbents
for
the silicones herein include clay, starch, kieselguhr, Fuller's Earth, and the
like.
The alkalinity of the solid sorbents is of no consequence to the compositions
herein, inasmuch as it has been discovered that the silicones are stable
io when admixed therewith. As disclosed hereinabove, the sorbent-plus-silicone
suds controlling agent must be coated or otherwise incorporated into a carrier
material of the type hereinafter disclosed to effectively isolate the silicone
from
the detergent component of the instant compositions.
Yet another preferred type of silicone suds controlling agent herein
1s comprises a silicone fluid, a silicone resin and silica. The silicone
fluids useful in
such suds controlling mixtures are any of the types hereinabove disclosed, but
are preferably dimethyl silicones. The silicone "resins" used in such
compositions
can be any alkylated silicone resins, but are usually those prepared from
methylsilanes. Silicone resins are commonly described as "three-dimensional"
2o polymers arising from the hydrolysis of alkyl trichlorosilanes, whereas the
silicone
fluids are "two-dimensional" polymers prepared by the hydrolysis of
dichlorosilanes. The silica components of such compositions are microporous
materials such as the fumed silica aerogefs and xerogels having the particle
sizes and surface areas hereinabove disclosed.
2s The mixed silicone fluid/silicone resin/silica materials useful in the
present
compositions can be prepared in the manner disclosed in U.S. Pat. No.
3,455,839. These mixed materials are commercially available from the Dow
Corning Corporation. According to U.S. Pat. No. 3,455,839, such materials can
be described as mixtures consisting essentially of: for each 100 parts by
weight
30 of a polydimethylsiloxane fluid having a viscosity in the range from 2 x10-
5 to
1.5x10-3 m2s-'(20cs. to 1500cs.) at 25°C, (a) from 5 to 50, preferably
from 5 to 20,
parts by weight of a siloxane resin composed of (CH3)3Si0"~ units and Si02
units
in which the ratio of the (CH3)3SiO,n units to the Si02 units is within the
range of
from about 0.6/1 to about 1.2/1; and (b) from 1 to 10, preferably from 1 to 5,
parts
ss by weight of a solid silica gel, preferably an aerogel.
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13
Again, such mixed silicone/silicone resin/silica suds controlting agents
must be combined with a detergent-impermeable carrier material to be useful in
the compositions herein.
The silicone suds controlling agents of the aforementioned type is
s preferably incorporated within (i.e., coated, encapsulated, covered by,
internalized, or otherwise substantially contained within) a substantially
water
soluble, or water-dispersible, and non-hydroscopic carrier material which must
be
impermeable to detergents and alkalinity and which, itself, must be
substantially
nonsurface active. By substantially nonsurface active is meant that the
carrier
to material, itself, does not interact with the silicone material in such
fashion that the
silicone material is emulsified or otherwise excessively dispersed prior to
its
release in the wash water. I.e., the particle size of the silicone droplet
should be
maintained above 1, more preferably above 5 mm.
Of course, when preparing a dry powder or granulated detergent
is composition, it is preferable that the silicone suds controlling component
thereof
also be substantially dry and nontacky at ambient temperatures. Accordingly,
it is
preferred herein to use as the carrier material, or vehicle, plastic, organic
compounds which can be conveniently melted, admixed with the silicone suds
controlling agent, and thereafter cooled to form solid flakes. There are a
wide
2o variety of such carrier materials useful herein. Since the silicone suds
controlling
agent is to be releasably incorporated in the carrier, such that the silicone
is
released into the aqueous bath upon admixture of the composition therewith, it
is
preferred that the carrier material be water soluble. However, water-
dispersible
materials are also useful, inasmuch as they will also release the silicone
upon
2s addition to an aqueous bath.
A wide variety of carrier materials having the requisite
solubility/dispersibility characteristics and the essential features of being
substantially non-surface active, substantially non-hydroscopic and
substantially
detergent-impermeable are known. However, polyethylene glycol (PEG) which
3o has substantially no surface active characteristics is highly preferred
herein.
PEG, having molecular weights of from 1,500 to 100,000, preferably from 3,000
to 20,000, more preferably from 5,000 to 10,000 can be used.
Surprisingly, highly ethoxylated fatty alcohols such as tallow alcohol
condensed with at least about 25 molar proportions of ethylene oxide are also
3s useful herein. Other alcohol condensates containing extremely high
ethoxylate
CA 02345581 2004-04-20
14
proportions (25 and above) are also useful herein. Such high ethoxylates
apparently lack sufficient surface active characteristics to interact or
otherwise
interfere with the desired suds control properties of the silicone agents
herein. A
variety of other materials useful as the carrier agents herein can also be
used,
s e.g., gelatin; agar; gum arabic; and various algae-derived gefs.
A very preferred carrier material is a mixture of from 0.2% to 15%,
preferably from 0.25% to 5%, more preferably from 0.25% to 2% of fatty acids
containing from 10 to 30, preferabiy.from 14 to 20, more preferably from 14 to
16, carbon atoms and the balance PEG. Such a carrier material gives a more
~o desirable suds pattern over the duration of the washing process, providing
more
suds at the start and less suds at the end than PEG alone. The fatty acid
delays
the solubility of the suds suppressor particle and thereby delays the release
of
the silicone. Soap andlor wax may also be used in place of the fatty acid.
The preferred irregularly shaped particulate silicone suds controlling
~s component can be conveniently prepared in a highly preferred flake form by
admixing the silicone suds controlling agent with a molten carrier material,
mixing
to form the appropriate silicone droplet size, and flaking, e.g., by milling
or
extruding to form a thin sheet, cooling to solidify the carrier material, and
breaking the sheet into particles of the right size. In another preferred
process
2o thin films can be formed by cooling molten carrier material with the suds
suppressor dispersed therein on, e.g., a chill roll or belt cooler and then
breaking
said film into appropriate sized flakes. The thickness of the flake should be
from
0.05 to 0.15 cm, preferably from 0.05 to 0.1 cm. When this procedure is used,
the
silicone suds controlling agent is contained within the carrier material so
2s effectively that when this material is eventually admixed with, or
incorporated
into, a detergent composition, the silicone does not substantially come into
contact with the detergent surfactant ingredient.
In order to provide a granular, nontacky suds controlling component useful
in dry granular detergent compositions, the flake of the silicone suds
controlling
so agent and carrier material should be substantially solidified. This can be
achieved
by use of belt coolers and which quickly coot the sheets or flakes such that
the
carrier melt is hardened. Extrusion techniques can also be used.
It is to be recognized that the amount of carrier used to isolate the silicone
suds controlling agent herein from the detergent component of the compositions
3s herein is not critical. It is only necessary that enough carrier be used to
provide
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sufficient volume that substantially all the silicone can be incorporated
therein.
Likewise, it is preferred to have sufficient carrier material to provide for
sufficient
strength of the resultant granule to resist premature breakage. Generally,
above
a 2:1, preferably from 5:1 to 100:1, more preferably from 20:1 to 40:1, weight
s ratio of carrier to silicone suds controlling agent is employed.
The size of the particles of the suds controlling component used in the
present compositions is selected to be compatible with the remainder of the
detergent composition. The suds controlling components herein do not segregate
unacceptably within the detergent composition. In general, particles with a
io maximum dimension of from 600 to 2000, preferably from 800 to 1600 ~m are
compatible with spray-dried detergent granules. Therefore, the majority of the
particles should have these maximum dimensions. The majority of the particles
should have a ratio of the maximum to the minimum diameter of from 1.5:1 to
5:1, preferably from 1.5:1 to 4:1.
is Other alternative suds controlling components which can be releasably
incorporated in a carrier material besides silicone, include monocarboxylic
fatty
acids and soluble salts thereof. These typically have hydrocarbyl chains of 10
to
24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the
alkali metal salts such as sodium, potassium, and lithium salts, and ammonium
2o and alkanolammonium salts. Other suitable suds controlling components
include
high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid
esters
of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone) N-alkylated
amino triazines such as tri- to hexa-alkylmelamines or di- to tetra
alkyldiamine
chtortriazines formed as products of cyanuric chloride with two or three moles
of
2s 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.
In addition to the above-mentioned silicone foam suppressing component,
other delayed-release foam suppressing components may be used. For
3o example, an encapsulated antifoam composition having a suds controlling
agent
and the reaction product of (i) an alkylalkoxysilane; and (ii) a silicone
condensation cure catalyst wherein the suds controlling agent is encapsulated
by
the reaction product may be used. The method of making such preferred
encapsulated antifoam compositions are described in GB 2 318 355, published
3s on April 22, 1998, by General Electric Co. In another example, a homogenous
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16
rosinlsilicone mixture made from a mixture of liquid pofydimethyl siloxane
with
aqueous caustic soda solution and melted rosin can also be used as a delayed-
release foam suppressing component. Because the rosin/silicone mixture
becomes soluble at higher temperatures, such foam suppressing is especially
useful for the delayed-release in washing conditions in which the wash water
is
heated over time. See also GB 1340043, published December 5, 1978, by
Griffiths et. al.
In another example for a silicone based foam suppressing component,
the carrier for the suds controlling agent can be a solid particulate
structure of
to modified cellulose which is soluble in water, but dissolves at a relatively
stow rate
due to the swelling of the surface of the cellulose. For examples of a
preferred
process for making such foam suppressing components, please see US
4,894,177, Starch et al., granted January 16, 1990 to Dow Corning Corp. In yet
another example, a suds controlling agent can be enclosed in a microcapsule
is composed of a core and a shell of a polymer, so that there is a controlled
release
of the core material (suds controlling agent) by destruction of the polymer
shell
by the action of bases.
In another example, microcapsules can be used as a delayed-release
foam suppressing component. One preferred microcapsule is made by
2o polymerizing (i) more than 40% by weight of malefic anhydride, (ii) 0-99%
by
weight of at least one monoethylenically unsaturated monomer which is oil-
soluble and which is different from the monomers of malefic anhydride,
(iii) 0-80% by weight of crosslinking monomers which are oil soluble and
different from malefic anhydride which have at least two monoethylenically
2s unsaturated non-conjugated double bonds in the molecule, and (iv) 0-20% by
weight of water-soluble monoethylenically unsaturated monomers, the
percentages relating to the total amount of monomers (i) to (iv), in the oil
phase
of a stable oil-in-water emulsion in the presence of polymerization initiators
which
form free radicals, where the temperature of the polymerizing reaction mixture
30 may be continuously or periodically increased during the polymerization.
For a
detailed process description, see US 5,596,051, Jahns et. al., granted on
January 21, 1997 to BASF.
C. Detersive components
The detergent composition of the invention can comprise additional
3s detersive components known in the art. In addition, the foaming component
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17
and/or the delayed-release foam suppressing component may further contain
detersive components. The precise nature of these additional components, and
levels of incorporation thereof will depend on the physical form of the
composition, and the precise nature of the washing operation for which it is
to be
used.
The detergent compositions preferably contains one or more additional
detersive components selected from the group consisting of surfactants,
bleaches, alkali metal salt of silicate, builders, chelating agents, enzymes,
fillers,
soil suspending agents, optical brighteners, dispersants, soil release agents,
to photoactivated bleaches, dyes, dye transfer inhibitors, pigments, perfumes,
clay
softening system, cationic fabric softening agents, and mixtures thereof.
In particular, it can be preferred that the particles comprises at least one
or
more anionic surfactants and preferably one or more cationic surfactants, as
described herein. It can also be preferred that the particles also, or
alternatively
is comprise builder material and bleaching species, as described herein
The detergent compositions may contain one or more surfactants
selected from anionic, cationic, ampholytic, amphoteric and zwitterionic
surfactants or nonionic surfactants as described above, and mixtures thereof.
A
typical listing of these surfactants, is given in U.S.P. 3,929,678 issued to
Laughlin
2o and Heuring on December 30, 1975. Further examples are given in "Surface
Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A
list
of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy
on
March 31, 1981.
Anionic Surfactant
2s Any anionic surfactant useful for detersive purposes is suitable. Examples
include salts (including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine salts) of
the
anionic sulfate, sulfonate, carboxytate and sarcosinate surfactants. Anionic
sulfate surfactants are preferred.
3o 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 C12-C18 monoesters) diesters of sulfosuccinate (especially
saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids
3s and hydrogenated resin acids are also suitable, such as rosin, hydrogenated
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18
rosin, and resin acids and hydrogenated resin acids present in or derived from
tallow oil.
The anionic surfactant can be present at a level of 0.5% to 80%,
preferably at a level of from 3% to 60%, more preferably of from 5% to 35% by
weight of the composition or the particle. The ratio of the stabilising agent
to the
anionic surfactant is preferably from 1:20 to 20:1, more preferably from 1:6
to 6:1.
Anionic Sulfate Surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty
oleoyl
1o glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17
acyl-N-
(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and
is branched primary Cg-C22 alkyl sulfates, more preferably the C11-C15
branched
chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C10-C1 g alkyl sulfates which have been ethoxylated with
from
0.5 to 50 moles of ethylene oxide per molecule. More preferably, the alkyl
2o ethoxysulfate surfactant is a C11-Clg, most preferably C11-C15 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 alkyl ethoxysulfate surfactants. Such mixtures
have
2s been disclosed in PCT Patent Application No. WO 93/18124.
Anionic Sulfonate Surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of
C5-C20 linear or branched alkylbenzene sulfonates, alkyl ester sulfonates, in
particular methyl ester sulfonates, Cg-C22 primary or secondary alkane
3o suifonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfonates,
and any mixtures thereof
Anionic Carboxylate Surfactant
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19
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
s RO(CH2CH20)x CH2C00-M+ wherein R is a C6 to C1 g alkyl group, x ranges
from O to 10, and the ethoxylate distribution is such that, on a weight basis,
the
amount of material where x is 0 is less than 20 % and M is a cation. Suitable
alkyl polyethoxy polycarboxylate surfactants include those having the formula
RO-(CHR1-CHR2-O)X-R3 wherein R is a Cg to C1g alkyl group, x is from 1 to
~0 25, R1 and R2 are selected from the group consisting of hydrogen, methyl
acid
radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures
thereof,
and R3 is selected from the group consisting of hydrogen, substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
~s 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-
2o pentyl-1-heptanoic acid. Certain soaps may also be included as suds
suppressors.
Alkali Metal Sarcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (R1) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl
2s or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal ion.
Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form
of
their sodium salts.
Cationic Surfactant
Another preferred surfactant is a cationic surfactant, which may preferably
3o be present at a level of from 0.1 % to 60% by weight of the composition or
particle, more preferably from 0.4% to 20%, most preferably from 0.5% to 5% by
weight of the composition. When present, the ratio of the anionic surfactant
to
the cationic surfactant is preferably from 25:1 to 1:3, more preferably from
15:1 to
1:1. most preferably from 10:1 to 1:1 The ratio of cationic surfactant to the
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stabilising agent is preferably from 1:30 to 20:1, more preferably from 1:20
to
10:1.
Preferably the cationic surfactant is selected from the group consisting of
cationic ester surfactants, cationic mono-alkoxylated amine surfactants,
cationic
s bis-alkoxylated amine surfactants and mixtures thereof.
Cationic Mono-Alkoxylated Amine Surfactants
The optional cationic mono-alkoxylated amine surfactant for use herein,
has the general formula:
R\ /ApR4
\N+ X-
~R3
to
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from
about 6 to about 11 carbon atoms; R2 and R3 are each independently alkyl
is groups containing from one to about three carbon atoms, preferably methyl;
R4 is
selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as
chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical
neutrality; A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-
),
propoxy, butoxy and mixtures thereof; and p is from 1 to about 30, preferably
1 to
2o about 15, most preferably 1 to about 8.
Highly preferred cationic mono-alkoxylated amine surfactants for use
herein are of the formula
Rl /(CH2CH20)1-5 H
~N+/ XO
CH3/ \CH3
wherein R1 is Cg-C1g hydrocarbyl and mixtures thereof, preferably Cg-C14,
especiafiy Cg-C11 alkyl, preferably Cg and C10 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
so ethoxy (CH2CH20) units (EO) are replaced by butoxy, isopropoxy
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21
[CH(CH3)CH20] and [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or
mixtures of EO and/or Pr and/or i-Pr units.
Cationic Bis-Alkoxylated Amine Surfactant
The cationic bis-alkoxylated amine surfactant for use herein, has the
s general formula:
Rl /APR3
R2~ ~A,qR4
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to
about
io 11, most preferably from about 8 to about 10 carbon atoms; R2 is an alkyl
group
containing from one to three carbon atoms, preferably methyl; R3 and R4 can
vary independently and are selected from hydrogen (preferred), methyl and
ethyl,
X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like,
sufficient to provide electrical neutrality. A and A' can vary independently
and are
is each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CHZCH20-),
propoxy,
butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4
and
q is from 1 to about 30, preferably 1 to about 4, and most preferably both p
and
qare1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein
2o are of the formula
R\ +/CH2CH20H
N X
CH / 'CHZCH20H
3
wherein R1 is Cg-C1g hydrocarbyl and mixtures thereof, preferably Cg, Cg, C10,
C12, C14 alkyl and mixtures thereof. X is any convenient anion to provide
2s charge balance, preferably chloride. With reference to the general cationic
bis-
alkoxyiated 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.
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22
Other cationic bis-alkoxylated amine surfactants useful herein include
s
compounds of the formula:
1
R~ ~(CH2CH20~H
N+ X-
R2~ ~(CH2CH20)qH
wherein R1 is Cg-C1g hydrocarbyl, preferably C6-C14 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.
Other compounds of the foregoing type include those wherein the ethoxy
io (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.
Amohoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
is surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides
include
those compounds having the formula R3(OR4)xN0(R6)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 aikylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof;
2o x is from 0 to 5, preferably from 0 to 3; and each R5 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 C10-C1g alkyl dimethylamine oxide, and
C10-18 acylamido alkyl dimethylamine oxide. A suitable example of an alkyl
aphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured by Miranol, tnc.,
2s Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the particle of the
invention or the compositions containing the particle of the invention. These
surfactants can be broadly described as derivatives of secondary and tertiary
so amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives
of quaternary ammonium, quaternary phosphonium or tertiary sulfonium
compounds. Betaine and sultaine surfactants are exemplary zwitterionic
CA 02345581 2001-03-27
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23
surfactants for use herein. Suitable betaines are those compounds having the
formula R(R')2N+R2C00- wherein R is a C6-C1 g hydrocarbyl group, each R1 is
typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines
are C12-18 dimethyl-ammonio hexanoate and the C10-18 acylamidopropane (or
ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also
suitable for use herein.
Water-Soluble Builder Compound
The compositions preferably contain a water-soluble builder compound,
typically present at a level of from 1 % to 80% by weight, preferably from 10%
to
~0 70% by weight, most preferably from 20% to 60% by weight of the composition
or
particle.
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
is least two carboxylic radicals separated from each other by not more that
two
carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or
oligomeric in type although monomeric polycarboxylates are generally preferred
for reasons of cost and performance.
2o 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
2s carboxylates and the sulfinyl carboxylates. Polycarboxylates containing
three
carboxy groups include, in particular, water-soluble citrates, aconitrates and
citraconates as well as succinate derivatives such as the
carboxymethyioxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, and
3o aminosuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates,
3s 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
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24
Polycarboxylates containing sulfo substituents include the sulfosuccinate
derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in
U.S.
Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in
British
Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates
s containing up to three carboxy groups per molecule, more particularly
citrates.
Borate builders, as well as builders containing borate-forming materials
that can produce borate under detergent storage or wash conditions are useful
water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
io tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium
and potassium and ammonium pyrophosphate, sodium and potassium
orthophosphate, sodium polymeta/phosphate in which the degree of
polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
is The composition may contain a partially soluble or insoluble builder
compound, typically present at a level of from 1 % to 80% by weight,
preferably
from 10% to 70% by weight, most preferably from 20% to 60% weight of the
composition or particle.
Examples of largely water insoluble builders include the sodium
2o aluminosilicates. Suitable aluminosilicate zeolites have the unit cell
formula
Naz[(A102)z(Si02)y]. xH20 wherein z and y are at least 6; the molar ratio of z
to
y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more
preferably
from 10 to 264. The aluminosilicate material are in hydrated form and are
preferably crystalline, containing from 10% to 28%, more preferably from 18%
to
2s 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably synthetically derived. Synthetic crystalline aluminosificate 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.
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Preferred crystalline layered silicates for use herein have the general
formula
NaMSix02x+1.yH20
s
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type are disclosed
in
EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649
and DE-A-3742043. Herein, x in the general formula above preferably has a
io value of 2, 3 or 4 and is preferably 2. The most preferred material is s-
Na2Si205,
available from Hoechst AG as NaSKS-6.
Perhydrate Bleaches
An preferred additional components of the composition is a perhydrate
bleach, such as metal perborates, metal percarbonates, particularly the sodium
is 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 Peroxyacid Bleaching System
2o A preferred feature of compositions 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
2s peroxide include inorganic perhydrate bleaches, such as the perborate
bleach of
the claimed invention. In an alternative preferred execution a preformed
organic
peroxyacid is incorporated directly into the composition. Compositions
containing
mixtures of a hydrogen peroxide source and organic peroxyacid precursor in
combination with a preformed organic peroxyacid are also envisaged.
so Peroxvacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen
peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally
peroxyacid bleach precursors may be represented as
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26
s
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 80% by weight of the particle, more preferably from 5% to 45% by
weight, most preferably from 3% to 15% by weight of the 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
is within these classes are disclosed in GB-A-1586789. Suitable esters are
disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
Leaving Groua~s
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis reaction to occur within the optimum time frame (e.g., a wash
2o cycle). However, if L is too reactive, this activator will be difficult to
stabilize for
use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
Y R3 RsY
-O ~ ; -O ~ Y , and
-N-C-R -N N -N-C-CH-R4
R3 ' ~ , Rs Y '
I
Y
CA 02345581 2001-03-27
wo oonosa6 Pcnus98n ~ 020
27
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
, ,
O CH -O Y O
-o-C-R~ -N\ /'~NRa , -N\ /NR4
C C
O O
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
s
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing
from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon
atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4
may be substituted by essentially any functional group including, for example
~o alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or
alkyl
ammmonium groups.
The preferred solubilizing groups are -S03 M+, -CO -M+, -S04 M+,
-N+(R3)4X- and O<--N(R3)3 and most preferably -S03-M~ and -C02-M+
wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a
cation
is which provides solubility to the bleach activator and X is an anion which
provides
solubility to the bleach activator. Preferably, M is an alkali metal, ammonium
or
substituted ammonium cation, with sodium and potassium being most preferred,
and X is a halide, hydroxide, methylsulfate or acetate anion.
Alkyl Percarboxylic Acid Bleach Precursors
2o 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
2s in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl
ethylene diamine (TAED) is particularly preferred. The TAED is preferably not
CA 02345581 2001-03-27
WO 00/20546 PCT/US98/21020
28
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
s nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate
(ABS) and pentaacetyl glucose.
Amide Substituted Alkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including those of the following general formulae:
io
R1-CN-R2C-L R1N--C-R2-CL
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group
is containing 1 to 10 carbon atoms and L can be essentially any leaving group.
Amide substituted bleach activator compounds of this type are described in EP-
A-0170386.
Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on
2o perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds
include
the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the
benzoylation products of sorbitol, glucose, and all saccharides with
benzoylating
agents, and those of the imide type including N-benzoyl succinimide,
tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable
2s 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 Peroxyacid Precursors
30 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
CA 02345581 2004-04-20
29
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
s be a perbenzoic acid, or substituted derivative thereof, precursor compound
as
described hereinbefore. Alternatively, the peroxyacid precursor compound may
be an alkyl percarboxylic acid precursor compound or an amide substituted
alkyl
peroxyacid precursor as described hereinafter. Cationic peroxyacid precursors
are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757;
~0 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512,
458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic
peroxyacid precursors are described in WO 95/29160
and US Patent Nos. 5,686,015; 5,460,747; 5,578,136 and 5,584,888.
~s Suitable cationic peroxyacid precursors include any of the ammonium or
alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams, and monobenzoyltetraacetyl glucose benzoyi peroxides. Preferred
cationic peroxyacid precursors of the N-acylated caprolactam class include the
trialkyl ammonium methyfene benzoyl caprolactams and the trialkyl ammonium
2o methylene alkyl caprolactams.
Benzoxazin Organic Peroxy~acid 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
C O
I
N C-R~
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyi.
3o Preformed Organic Perox~racid
CA 02345581 2001-03-27
WO 00/20546 PCT/US98/21020
The organic peroxyacid bleaching system may contain, in addition to, or
as an alternative to, an organic peroxyacid bleach precursor compound, a
preformed organic peroxyacid , typically at a level of from 1 % to 15% by
weight,
more preferably from 1 % to 10% by weight of the composition. A preferred
class
of organic peroxyacid compounds are the amide substituted compounds of the
following general formulae:
R1-C-N-R2-C-OOH R1-NC-R2-C-OOH
O R5 O or R5 O O
io wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon
atoms, R2 is
an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon
atoms,
and R5 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,
is 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
2o The compositions optionally contain a transition metal containing bleach
catalyst. One suitable type of bleach catalyst is a catalyst system comprising
a
heavy 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 rations, and a sequestrant having defined
2s stability constants for the catalytic and auxiliary metal rations,
particularly
ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic
acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S.
Pat.
4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in IJ.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, Mnlll2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
(C104)2,
MnIV4(u-O)6(1,4,7-triazacyclononane)4-(C104)2; MnIIIMnIV4(u-O)1(u-OAc)2_
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31
(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)3, and mixtures thereof.
Others
are described in European patent application publication no. 549,272. Other
ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-
triazacyclododecane,
2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-
s tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
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_(PFg). Still another type of bleach catalyst, as
io 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. Other examples include
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands,
including
N4Mnlll(u_O)2MnIVN4)+and [BipY2Mnlll(u_O)2MnIVbipY21-(C104)3~
is Further suitable bleach catalysts are described, for example, in European
patent application 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
2o 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
2s cations), and U.S. 4,728,455 (manganese gluconate catalysts).
Heavy Metal Ion Sequestrant
The composition preferably contain as an optional component a heavy
metal ion sequestrant. By heavy metal ion sequestrant it is meant herein
components which act to sequester (chelate) heavy metal ions. These
so 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 20%, preferably from 0.1 % to 10%, more preferably
from
0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the
3s compositions or particle. Suitable heavy metal ion sequestrants for use
herein
CA 02345581 2001-03-27
WO 00!20546 PCTNS98/21020
32
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 yenta
s (methylene phosphonate}, ethylene diamine tri (methylene phosphonate)
hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1
diphosphonate. Other suitable heavy metal ion sequestrant for use herein
include nitrilotriacetic acid and polyaminocarboxylic acids such as
ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,
io ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-
hydroxypropylenediamine disuccinic acid or any salts thereof. Especially
preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal,
alkaline earth metal, ammonium, or substituted ammonium salts thereof, or
mixtures thereof.
~s 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-
2o 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.
2s 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.
3o En. zyrme
Another preferred ingredient useful in the composition is one or more
additional enzymes. Preferred additional enzymatic materials include the
commercially available lipases, cutinases, amylases, neutral and alkaline
proteases, esterases, cellulases, pectinases, lactases and peroxidases
3s conventionally incorporated into detergent compositions. Suitable enzymes
are
CA 02345581 2004-04-20
33
discussed in US Patents 3,519,570 and 3,533,139. Preferred commercially
available protease enzymes include those sold under the trademarks Alcalase,
Savinase, Primase, Durazym, and Esperase by Novo Industries AIS (Denmark),
those sold under the trademarks Maxatase, Maxacal and Maxapem by Gist-
Brocades, those sold by Genencor International, and those sold under the
trademarks 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
~o 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 trademark Rapidase by Gist-Brocades, and those sold under the
trademarks Termamyl and BAN by Novo Industries A/S. Amylase enzyme may
be incorporated into the composition in accordance with the invention at a
level
is of from 0.0001% to 2% active enzyme by weight of the composition.
Lipotytic enzyme may be present at levels of active fipolytic enzyme of
from 0.0001 % to 10% by weight of the particle, preferably 0.001 % to 3% by
weight of the composition, most preferably from 0.001 % to 0.5% by weight of
the
compositions.
2o The lipase may be fungal or bacterial in origin being obtained, for
example, from a lipase producing strain of Humicola sp., Thermomyces sp. or
Pseudomonas sp. including Pseudomonas pseudoalcali e~L nes or Pseudomas
fluorescens. Lipase from chemically or genetically modified mutants of these
strains are also useful herein. A preferred Lipase is derived from Pseudomonas
2s pseudoalcaligenes, which is described in Granted European Patent, EP-B-
0218272.
Another preferred lipase herein is obtained by cloning the gene from
Humicola lanuginosa and expressing the gene in Aspergillus o za, as host, as
described in European Patent Application, EP-A-0258 068, which is commercially
3o available from Novo Industri A/S, Bagsvaerd, Denmark, under the trademark
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 in compositions. By organic
3s polymeric compound it is meant herein essentially any polymeric organic
CA 02345581 2001-03-27
WO 00/20546 PCTNS98/21020
34
compound commonly used as dispersants, and anti-redeposition and soil
suspension agents in detergent compositions, including any of the high
molecular
weight organic polymeric compounds described as clay flocculating agents
herein.
Organic polymeric compound is typically incorporated in the detergent
compositions of the invention at a level of from 0,1% to 50% by weight of the
particle, preferably from 0.5% to 25%, most preferably from 1 % to 15% by
weight
of the compositions.
Examples of organic polymeric compounds include the water soluble
~o organic homo- or co-polymeric polycarboxylic acids or their salts in which
the
polycarboxylic acid comprises at least two carboxyl radicals separated from
each
other by not more than two carbon atoms. Polymers of the latter type are
disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt
2000-5000 and their copolymers with malefic anhydride, such copolymers having
is a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
The
polyamino compounds are useful herein including those derived from aspartic
acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic
acid, polyaspartic acid and vinyl alcohol, particularly those having an
average
2o molecular weight of from 5,000 to 10,000, are also suitable herein. Other
organic
polymeric compounds suitable for incorporation in the detergent compositions
herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
Another organic compound, which is a preferred clay dispersant/ anti-
2s redeposition agent, for use herein, can be the ethoxylated cationic
monoamines
and diamines of the formula:
H3 I H3
X-~- OCH2CH2)n i +- CH2 - CH2 -(- CH2)a b i +- CH2CH20 ~ X
(CH2CH20 ~ X (CH2CH20 ~ X
3o wherein X is a nonionic group selected from the group consisting of H, C1-
C4
alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0
to
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WO 00/20546 PCTNS98/21020
20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or
0;
for cationic monoamines (b=0), n is at least 16, with a typical range of from
20 to
35; for cationic diamines (b=1), n is at least about 12 with a typical range
of from
about 12 to about 42.
s Other dispersants/ anti-redeposition agents for use herein are described in
EP-B-011965 and US 4,659,802 and US 4,664,848.
Clay Softening System
The compositions may contain a clay softening system comprising a clay mineral
compound and optionally a clay flocculating agent. The clay mineral compound
is
io preferably a smectite clay compound. Smectite clays are disclosed in the US
Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European
Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and
Gamble Company describe suitable organic polymeric clay flocculating agents.
Polymeric Dye Transfer Inhibiting Agents
is The particles or compositions herein may also comprise from 0.01% to 10
%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer
inhibiting
agents. The polymeric dye transfer inhibiting agents are preferably selected
from
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
2o a) Polyamine N-oxide a~olymers
Polyamine N-oxide polymers suitable for use herein contain units having
the following structure formula
P
(I) Ax
E
R
2s
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
CA 02345581 2001-03-27
WO 00/20546 PCT/US98/2102b
36
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups
or any combination thereof whereto the nitrogen of the N-O group can be
attached or wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general
s structures
O
O
(R1) x _N_(R2)Y 1
(Rg)z or N_(R1 )x
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
io groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein
the
nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O
group forms part of these groups. The N-O group can be part of the
polymerisable unit (P) or can be attached to the polymeric backbone or a
combination of both:
is Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected from
aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said
polyamine
N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the
N-O group forms part of the R-group. Preferred polyamine N-oxides are those
2o wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole,
pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the
N-O group is attached to the polymerisable unit. A preferred class of these
polyamine N-oxides comprises the polyamine N-oxides having the general
2s formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups
wherein the
nitrogen of the N-O functional group is part of said R group. Examples of
these
classes are polyamine oxides wherein R is a heterocyclic compound such as
pyrridine, pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of
3o polymerisation. The degree of polymerisation is not critical provided the
material
CA 02345581 2001-03-27
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37
has the desired water-solubility and dye-suspending power. Typically, the
average molecular weight is within the range of 500 to 1000,000.
b) Copolymers of N-vin~pyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone
having an average molecular weight range of from 5,000 to 50,000. The
preferred copotymers have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone
from 1 to 0.2.
c,~ Polyvinylpyrrolidone
The compositions herein may also utilize polyvinylpyrrolidone ("PVP")
to having an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP Corporation, New
York,
NY and Montreal, Canada under the product names PVP K-15 (viscosity
molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000},
PVP K-60 (average molecular weight of 160,000}, and PVP K-90 (average
is molecular weight of 360,000). PVP K-15 is also available from ISP
Corporation.
Other suitable polyvinylpyrrolidones which are commercially available from
BASF
Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone
The compositions herein may also utilize polyvinyloxazolidones as
zo polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have
an
average molecular weight of from 2,500 to 400,000.
e) Polyvinylimidazole
The compositions herein may also utilize polyvinylimidazole as polymeric
dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an
2s average molecular weight of from 2,500 to 400,000.
Optical Brightener
The compositions herein also optionally contain from about 0.005% to 5%
by weight of certain types of hydrophilic optical brighteners. Hydrophilic
optical
brighteners useful herein include those having the structural formula:
R1 Rz
N H H N
N O~--N O C C O
H H
RZ S03M S~3M R~
CA 02345581 2004-04-20
38
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,
morphitino, chloro and amino; and M is a salt-forming cation such as sodium or
s potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and
M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-
bis-
hydroxyethyl)-s-triazine-2-yl)aminoj-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
trademark
~o Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-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'-
~s stilbenedisulfonic acid disodium salt. This particular brightener species
is
commercially marketed under the trademark Tinopai 5BM-GX by Ciba-Geigy
Corporation. When in the above formula, R1 is anilino, R2 is morphilino and M
is
a ration such as sodium, the brightenec is 4,4'-bis[(4-anilino-6-morphilino-s-
triazine-2-yl)aminoj2,2'-stilbenedisulfonic acid, sodium salt. This particular
2o brightener species is commercially marketed under the trademark Tinopal AMS-
GX by Ciba Geigy Corporation.
Cationic Fabric Softening Agents
Cationic fabric softening agents can also be incorporated into
compositions in accordance with the present invention. Suitable cationic
fabric
2s softening agents include the water insoluble tertiary amines or dilong
chain
amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340. Cationic
fabric softening agents are typically incorporated at total levels of from
0.5% to
15% by weight, normally from 1 % to 5% by weight.
pH of the Compositions
3o The detergent compositions preferably can have an acidic or an alkaline
pH, depending on the application or the additional ingredients. It may be
preferred that the particles or the compositions have a pH, measured as a 1
solution in distilled water, of at least 3.0, preferably from 4.0 to 12.5.
D. Laundry Methods
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39
In a manual laundry method, the method typically comprises contacting
and/or treating soiled fabric with an aqueous wash solution containing
detergent
composition in a bucket or a container with a solid bar. The consumer contacts
the solid bar with the soiled fabric by scrubbing. After all the fabric has
been
s scrubbed, fresh water is added to the container and the fabrics are rinsed.
This
rinsing process may be repeated. During a typical manual laundry method, a
cleaning or scrubbing implement may also be used.
In a machine laundry method, the method typically comprises treating
soiled laundry with an aqueous wash solution containing detergent composition
io having dissolved or dispensed therein an effective amount of detergent
composition. Preferably, an effective amount is from about 10g to about 300 g
or
product dissolved or dispersed in a wash solution of volume from about 5 to 65
litres.
In a method or soaking fabrics, soiled fabrics are immersed in an aqueous
is soaking solution containing detergent composition for an effective period
of time.
Then, the fabrics are removed from the soaking solution.
EXAMPLES
The following examples further describe and demonstrate embodiments
within the scope of the present invention. The examples are given solely for
the
2o purpose of illustration and are not to be construed as limitations of the
present
invention, as many variations thereof are possible without departing from the
spirit and scope of the invention.
In the following Examples all levels are quoted as % by weight of the
composition. The following examples are illustrative of the present invention,
but
2s are not meant to limit or otherwise define its scope. All parts,
percentages and
ratios used herein are expressed as percent weight unless otherwise specified.
Abbreviations used in Examples
In the exemplified foaming systems and cleaning compositions, the abbreviated
so component identifications have the following meanings:
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS : Sodium C14-C15 linear alkyl sulfate
3s MES : a-sulpho methylester of C1g fatty acid
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CxyEzS : Sodium C1x-C1y branched alkyl sulfate condensed
with z moles of ethylene oxide
MBASx, y : Sodium mid-chain branched alkyl sulfate
having an average of x carbon atoms, whereof
an
s average of y carbons comprised in (a) branching
units)
C4g SAS : Sodium C14-C1g secondary alcohol sulfate
SADExS : Sodium C14-C22 alkyl disulfate of formula
2-(R).C4
H7-1,4-(S04-)2 where R = C 1 pOC 1 g, condensed
with
io z moles of ethylene oxide
CxyEz : A C1x-1y branched primary alcohol condensed
with
an average of z moles of ethylene oxide
QAS I : R2.N+(CH3)2(C2H4OH) with R2 = 50%-60% Cg;
40%-50% C11
~s QAS II : R1.N+(CH3)(C2H40H)2 with R1 = C12-C14
Soap : Sodium linear alkyl carboxylate derived from
an 80/20
mixture of tallow and coconut oils.
TFAA I : C12-C14 alkyl N-methyl glucamide
TFAA II : C1g-C1g alkyl N-methyl glucamide
2o TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
Zeolite A I : Hydrated Sodium Aluminosilicate of formula
Nal2(A102SiO2)12. 27H20 having a primary particle
size in the range from 0.1 to 10 micrometers
2s Zeolite A II : overdried Zeolite A I
NaSKS-6 : Crystalline layered silicate of formula b
-Na2Si205
Citric acid I : Anhydrous citric acid
Citric acid II : Citric acid monohydrate
Malic acid : Anhydrous malic acid
so Mafeic acid : Anhydrous malefic acid
Aspartic acid : Anhydrous aspartic acid
Carbonate I : Anhydrous sodium carbonate with an average
particle
size between 200pm and 900pm
Carbonate II : Anhydrous sodium carbonate with an average
particle
3s size between 100p,m and 200p,m
CA 02345581 2004-04-20
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Bicarbonate : Anhydrous sodium bicarbonate with a particle
size
distribution between 400pm and 1200~m
Silicate : Amorphous Sodium Silicate (Si02:Na20; 2.0
ratio)
Sodium sulfate : Anhydrous sodium sulfate
s Citrate : Tri-sodium citrate dihydrate of activity
86.4% with a
particle size distribution between 425~.m
and q 850~m
MA/AA : Copolymer of 1:4 maleidacrylic acid, average
molecular weight about 70,000
CMC : Sodium carboxymethyt cellulose
io Protease : Proteolytic enzyme of activity 4KNPU/g sold
by NOVO
Industries AlS under the trademark Savinase
Alcalase : Proteolytic enzyme of activity 3AU/g sold
by NOVO
Industries A!S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g
sold by
t5 NOVO Industries AlS under the trademark Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold
by NOVO
Industries AIS under the trademark Termamyl
60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold
by NOVO
Industries AIS under the trademark Lipolase
2o Endolase : Endoglunase enzyme of activity 3000 CEVUIg
sold by
NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
PB1 : Anhydrous sodium perborate bleach of nominal
2s formula NaB02.H202
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03.3H2O2
NAC-OBS : (Nonanamido caproyl) oxybenzene sulfonate in the
fom~ of the sodium salt.
3o NOBS : Nonanoyl oxybenzene sulfonate in the form of the
sodium salt
DPDA : Diperoxydodecanedioic acid
PAP : N-phthaioylamidoperoxicaproic acid
NAPAA : Nonanoylamido peroxo-adipic acid
ss NACA : 6 nonylamino - 6 oxo - capronic acid.
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TAED : Tetraacetylethylenediamine
DTPMP : Diethylene triamine yenta (methylene phosphonate),
marketed by Monsanto under the Trademark
bequest 2060
s Photoactivated : Suifonated Zinc or aluminium Phthlocyanine
encapsulated
Brightener 1 : Disodium 4,4'-bis(2-suiphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis{4-anilino-6-morpholino-1.3_5-triazin-
2-yl)amino) stilbene-2:2'-disulfonate.
~o HEDP : 1,1-hydroxyethane diphosphonic acid
PVNO : Poiyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole
QEA : bis ((C2H50)(C2H40}n) (CH3) -N+-C6H12-N+- {CH3)
bis ((C2H50}-(C2H40)n), wherein n=from 20 to 30
is SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy
and terephthaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short
block polymer
Delayed-release : A flake material containing about 10%, by weight, of
2o foam suppressing silicone/silica fluid and 90% by weight, of polyethylene
comp. 1 glycol having a molecular weight of about 8,000. The
flake material has a particle size of 2000 microns to
about 500 microns (-10/+35 Tyler mesh).
Delayed-release : A flake material containing about 10% by weight of
2s foam suppressing siliconeJsilica fluid, about 0 to 7% by weight of palmitic
comp. 2 acid or Hyfac~ fatty acids, and the balance
polyethylene glycol having a molecular weight of
about 8,000. The flake material has a particle size of
2000 microns to about 500 microns (-10!+35 Tyler
3o mesh).
Suds Booster: One or a mixture of polyethylene glycol, amine oxide,
monoethanot amine, diethanol amine, fatty alcohol,
sugar, protein and betaine.
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43
In the following Examples all levels are quoted as parts per weight of the
composition:
Controlled Foaming System Examples
s
The following examples exemplify foaming systems in accord with the
invention, each of which, or mixtures thereof, can be used in detergent
compositions.
The controlled foaming system of the present invention can be made by
to any method known in the art for formation of particles, as described above.
In the foaming system, there are many variations of how the foaming
component and the delayed-release foam suppressing component may be
combined. For example, the foaming component and the foam suppressing
component may be agglomerated or otherwise mixed together with other optional
is components to form one solid particle. In addition, the foaming component
and
the foam suppressing component may be two separate particles. Either the one
solid particle or the two separate particles making up the foaming system may
be
used in detergent compositions.
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44
Example 1
Foaming Systems A to J
A B I ~ E F ~ ! i j
C D G H I J
TFAA I/ TFAAI 31.028.0! ~ 13.0__ _ a ~ ~
I 11.027.5 15.0_ 15.0- 10.0
~ I
22.0
C24E31C24E5 - - 128.0, 25.022.0- ~ X10.010.0
- ~ 5.0 r
i t
PEG4000 5.0 5.3 ~ I - - '7.0l5.OE 5.0
- 5.0 i -
i i
citric acid I 13.514.0~ I 16.0~ ! ! t E
20.015.5 15.015.010.0- 10.0
i ~ i ~ i
'
Malefic acid - - ~ - - - - ~ I 10.0
- - 10.5
sodium carbonate 13.5- ~ ~ - - - ~ ~ E
I 20.0- 15.010.0
sodium carbonate - 14Ø 6.0 14.010.0;10.0;10.05.0~
II - -
sodium bicarbonate- - - 6.0 - - 10.0;- 5.55.0
~ ~ ~ ( '
j t
i ~ i
Zeolite A I I 18.035.7120.018.0 - 9.0 10.05.0 14.017.0
! i ~ ! ~ ~
i
'
LAS 9.0 - - - 12.0- - 10.0- 13.0
~ , ' ;
QAS I/ QAS II 9.0 - - - - - 6.0 3.0 - -
, i ~ ,
TAED/ NOBS/ - - - 19.0 10.0- - 2 _ -
NACA-OBS ~ ~ ~ ~ 0.0
i ~ t
Perborate/ - - - - - 19.0- 10.0- -
percarbonate i ~ ~ !
,
' i ~
Foam supp. 1.0 3.0 - - 10.0- 10.01- - 5.0
~ ~ ! "
Component 1
r
Foam supp. - - 1.0 3.0 10.0;- 10.010.05.0
Component 2 ~ j ~ ~
,
iSuds Booster - - - - - - _
~ 10.010.010.0
~
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Foaming systems A-J produces upon contact with water gas bubbles
having an average bubble particle size of about 400 microns or less, and the
foam suppressing components reduces the water gas bubbles as soon as the
mixture is agitated. The bubbles have been reduced at least about 40% to about
70% after about 6 to 10 minutes after the mixture is first agitated.
The following examples exemplify cleaning compositions comprising the
foaming component of the invention:
Example 2
io The following are high density and bleach-containing detergent
formulations according to the present invention (can be for either granular
form or
tablet form):
a b c
Blown Powder
Zeolite A 5.0 5.0 15.0
Sodium sulfate 0.0 5.0 0.0
LAS 20.0 30.0 20.0
C45AS 3.0 5.0 20.0
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
Foaming System A 20.0
Foaming System B - 15.0 -
Foaming System G - - 10.0
Spray On (on particles)
Encapsulated Perfume 0.3 0.3 0.3
C25E3 - - 2.0
Dry additives
Q~ - - 0.5
Citrate 5.0 - 2.0
Bicarbonate - 3.0 -
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46
Carbonate 8.0 10.0 5.0~
NAC OBS 6.0 - -
Manganese catalyst - - 0.3
NOBS - 2.0 -
PB1 14.0 7.0 -
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Citric acid - - 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Suds Booster 5.0 1.0 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) 750 800 700
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WO 00/20546 PCTNS98/21020
47
s
Examele 3
The following are high density detergent formulations according to the present
invention:
d a
Foaming System A 45.0
Foaming System H 60.0
Spra On
C25E3 - 1.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13:0 10.0
Citrate - 1.0
NAC OBS 4.1 -
TAED 0.8 -
Percarbonate 20.0 5.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Amylase 0.6 0.6
QEA 1.0 -
Suds Booster 5.0 -
Bri htener 1 0.2 0.2
Brightener 2 0.2 -
Densi (g/litre) 700 850
It is understood that the examples and embodiments described herein are
for illustrative purposes only and that various modifications or changes in
light
thereof will be suggested to one skilled in the art without departing from its
spirit
to and scope.
