Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS OF CLEANING CARPETS WITH A COMPOSITION COMPRISING A
POLY (VINYL METHYL ETHER / MALEIC ACID) COPOLYMER
Technical Field
The present invention relates to a process of cleaning carpets using a liquid
composition. More particularly, the present invention relates to a process of
cleaning carpets whereby carpet cleaning and/or carpet anti-resoiling benefits
are
provided.
Background of the Invention
Carpets produced from synthetic or natural fibers and mixtures thereof are
commonty used in residential and commercial applications as a floor covering.
Various types of fbers can be used in making carpets such as polyamide fibers,
polyester fibers as well as wool, cotton or even silk in the case of rugs.
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However, carpets irrespective of whether they are made from natural or
synthetic
fibers are all prone to soiling and staining when contacted with many
household .
items. Food, grease, oils, beverages in particular such as coffee, tea and
soft
drinks especially those containing acidic dyes can cause unsightly, often dark
stains on carpets. Also fibers may become soiled as a result of dirt
particles, clay,
dust, i.e., particulate soils in general, coming into contact with and
adhering to
the fibers of the carpet. These latter soils often appear in the form of a
diffuse
layer of soils rather than in the form of spots and tend to accumulate
particularly
in the so called "high traffic areas" such as near doors as a result of
intensive use
of the carpets in such areas.
Compositions for cleaning carpets are already known in the art. For example as
disclosed in EP-A-7b1 213.
However, it is understood that consumers have a need for a carpet cleaning
product delivering anti-resoiling benefits to the carpets treated therewith.
Indeed,
consumers are looking for liquid carpet cleaning compositions that would
render
a carpet first treated therewith, less prone to soiling and thus facilitate
the next-
time cleaning operation.
Thus, the objective of the present invention is to provide a process for
cleaning a
carpet with a liquid carpet cleaning composition that will impart anti-
resoiiing
properties to a carpet treated therewith.
Furthermore, it is an objective of the present invention to provide a process
of
cleaning a carpet which provides excellent overall cleaning performance on
various types of stains including particulate stains, greasy stains,
bieachable
stains and/or enzymatic stains.
It has now been found that the above objectives can be met by a process of
cleaning a carpet with a liquid composition comprising a poly (vinyl methyl
ether /
malefic acid) copolymer as an anti-resoiling agent.
An advantage of the process of cleaning carpets according to the present
invention is that said process provides an easy and fast way for a user to
clean a
carpet, while providing excellent overall cleaning performance. More
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advantageously, the process of cleaning carpets according to the present
. invention provides excellent cleaning performance, when both used to clean
the
whole carpet or localized carpet stains. In addition to this, this process
does not
result in tacky residues being left on carpets after treatment. The presence
of
tacky residues has been found to increase re-soiling since soils can stick to
the
residues.
Advantageously, excellent cleaning performance is obtained on different types
of
stains and soils, including enzymatic stains as well as particulate stains
and/or
greasy stains, especially in highly soiled, so called "high traffic areas".
A further advantage of the present invention is that the process of cleaning
carpets herein is applicable to all carpet types, especially delicate natural
fibers.
The present invention is also suitable to be used to clean hard wearing
textiles
and fabrics, e.g., upholstery, rugs, curtains.
Yet another advantage of the process of cleaning carpets and of the
compositions of the present invention is that they may be applied directly on
the
carpet without causing damage to the carpet. In particular, the compositions
used
in the present process are safe to all known carpet dyes, even well known
particularly sensitive natural dyes.
Back. rq ound art
The following documents are representative of the prior art available on
carpet
cleaning compositions.
EP-A-751 213 discloses a carpet cleaning composition comprising salicylic acid
and a compound selected from the group consisting of amine oxides, soil
suspending polycarboxylate or polyamine polymers, hydroxy-pyridine N-oxides,
. chelating agents and mixtures thereof. However, poly (vinyl methyl ether /
malefic
acid) copolymers are not disclosed therein.
Summary of the Invention
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The present invention encompasses a process of cleaning a carpet with a liquid
composition comprising a poly (vinyl methyl ether / malefic acid) copolymer.
In a preferred embodiment said composition further comprises a peroxygen
bleach.
In another preferred embodiment said composition comprises a further anti-
resoiling agent, preferably a polyamine polymer, more preferably an
alkoxylated
poiyamine polymer.
In still another preferred embodiment said composition further comprises a
surfactant, preferably an anionic surfactant, a zwitterionic surfactant or a
mixture
thereof, most preferably a sarcosinate surfactant.
The present invention also encompasses the use of a poly (vinyl methyl ether /
malefic acid) copolymer as an anti-resoiling agent in a carpet cleaning
composition to clean carpets whereby said carpet cleaning composition provides
carpet cleaning and/or carpet anti-resoiling benefits.
Detailed Description of the Invention
Process of cleaning a carpet
The present invention encompasses a process of cleaning a carpet with a liquid
composition comprising a poly (vinyl methyl ether / malefic acid) copolymer.
Preferably, said process comprises the steps of applying said composition to
the
surface of the carpet and leaving said composition to substantially dry onto
the
carpet. More preferably said process of cleaning a carpet further comprises
the
step of removing said composition, even more preferably said process of .
cleaning a carpet further comprises the step of removing said composition in
combination with soil particles.
In a preferred embodiment of the present invention a liquid composition
according to the present invention is applied onto the carpet by using a
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dispensing device, preferably a spray dispenser. Said spray dispenser is a
container that has at least one aperture through which the composition is
dispensed to produce a spray of droplets.
Such a spray dispenser may comprise a means for delivering the composition by
a pump ("pump spray dispenser") or may be operated by any source of
pressurised gas such as an aerosol-can or a pressurizes. Pump spray dispensers
may be manually operated or electrically operated. Said spray dispensers are
particularly preferable if a large area is to be treated as they facilitate
the ease of
use by the consumer. Said spray dispensers ensure uniform coverage of the
area to be treated. Furthermore, said spray dispensers optimise the action
time
of the composition as the application of product by spraying best allows the
product to be left to substantially dry on the area treated in an acceptable
amount
of time, preferably even without rubbing or brushing.
Preferred spray dispensers herein are manually or electrically operated pump
spray dispensers. Typical manually operated pump spray dispensers include
push button operated or trigger operated pump spray dispenser. A preferred
spray dispenser herein is a container wherein the means for delivering the
composition comprises an electrically driven pump and a spray arm. Said spray
arm is either extended or extendible and has at least one aperture so that in
operation, the composition is pumped by said electrically driven pump from the
container, through the spray arm to the aperture from which it is dispensed.
It is
preferred that the spray arm communicates with the container by means of a
flexible connector. The spray arm may have at least one aperture located along
its length. The spray arm makes it easier to control where the composition is
sprayed and therefore, the accuracy with which the composition is applied is
increased. The electrically driven pump may be, for example, a gear pump, an
impeller pump, a piston pump, a screw pump, a peristaltic pump, a diaphragm
pump, or any other miniature pump. In a highly preferred embodiment of the
. electrically driven pump for use herein the pump is a gear pump with a
typical
speed between 6000 rpm and 12000 rpm. The electrically driven pump is driven
by a means such as an electric motor which typically produces a torque between
1 and 20 mN.m. The electric motor must in turn be provided with a power
source.
The power source may be either main electricity (optionally via transformer),
or it
may be a throw-away battery or rechargeable battery. The spray arm may be
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rigidly extended. However such a spray arm can be difficult to store, and the
spray arm is preferably extensible either by means of telescopic or foldable
configuration.
In a highly preferred embodiment, the composition is applied onto the carpet
in
the form of a spray of droplets having a particle size distribution with a
mean
diameter D(v,0.9) of less than 1500 microns, preferably less than 1000
microns,
more preferably of less than 750 microns, even more preferably less than 500
microns, and most preferably from 350 microns to 10 microns.
By "mean diameter D(v,0.9) of less than 1500 microns" for a droplet size
distribution it is meant that 90% of the spray of droplets dispensed
(expressed in
volume unit) has a droplet diameter of less than 1500 microns. For instance, a
D(v,0.9) of less than 1500 microns indicates that 90% of the total sprayed
volume
is dispensed with droplets whose diameter is less than 1500 microns.
The particle size distribution of a spray of droplets can be determined by
following the procedure detailed herebelow:
A suitable test equipment is the Malvern Mastersizer S LongBed~ with 1000 mm
lens and a maximum particle size range of 3475 microns. The Malvern
Mastersizer S LongBed~ provides a 21 cm opening (between its lenses) to
accommodate spray flow. In all readings at the Malvern, the lens surface must
remain free of spray contamination. In the present setup procedure, the
distance
from the aperture of the spray dispenser to the laser was fixed at 8 cm, this
to
minimize lens contamination. At 8 cm distance, the spray was directed to the
laser beam to place the laser center to the spray cone. At least three
readings
have to be made for each composition sprayed to determine the particle size
distribution of the spray of droplets. The spray dispenser to be used in the
test
according to the present invention is an electrically operated spray
dispenser,
preferably a battery-operated system. If a battery-operated system is used, a
"Full charge test" is being performed. By "Full charge test" it is meant
herein, that
the current was held consistent by connecting the battery-operated spray
dispenser to a 3.9 voltage direct current (vdc) from an external power supply,
this
ensures a constant spray force. A comparative spray dispenser used herein is a
hand-held trigger-operated spray dispenser. Hand-held trigger-operated systems
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have to be tested repeatability with three different persons. These persons
are
chosen for their varied ability to actuate the trigger against force: Small
female,
female with strong finger strength, and medium male.
Any container adapted to deliver a spray of droplets as defined herein is
suitable
for use herein. Several modifications can be made to the conventional, single
aperture, spray head to ensure that a spray of such droplets as required
herein is
formed.
The amount of the compositions for the cleaning of carpets according to the
present invention applied will depend on the severity of the stain or soil. in
the
case of stubborn stains more than one application may be required to ensure
complete removal of the stain.
The area to be cleaned by applying the compositions according to the present
invention may be of any size. Indeed, a complete section or more preferably
the
whole carpet may be treated with the composition for the cleaning of carpets
according to the present invention.
In a process of cleaning a carpet according to a preferred embodiment of the
present invention the step of applying a composition onto the carpets as
described herein before, does not need to be followed by a step where manual
action is required other than the final optional removing step. Indeed the
compositions herein allow excellent cleaning performance without requiring any
manual action like rubbing and/or brushing. An advantage of the present
invention is that the cleaning action of the present composition commences as
soon as said compositions are applied onto said carpet.
In a preferred embodiment, the composition applied to the carpet is left to
substantially dry. Typically, the composition is left to dry on the carpet for
less
than 2 hour, preferably less than 1 hour, more preferably less than 40
minutes,
even more preferably from 1 to 30 minutes and most preferably from 1 to 20
minutes.
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By "substantially dry" it is meant herein the stage where at least 40%,
preferably
at least 60% of the initial amount of composition dispensed onto the carpet is
lost
due to evaporation.
Indeed, said composition may be left to substantially dry until said
composition
combined with dirt forms substantially dry residues. Preferably, said
composition
more preferably said substantially dry residues, are then removed from the
carpet. Even more preferably said substantially dry residues are removed
mechanically, most preferably by vacuum cleaning. This may be carried out with
the help of any commercially available vacuum cleaners like for instance a
standard Hoover~ 1300W vacuuming machine.
According to the present invention the compositions herein may be used for the
removal of stains and soils as well as of odors from carpets or hard wearing
textiles and fabrics, e.g., upholstery. In addition the compositions according
to
the present invention may be used to hygienise, disinfect and/or exterminate
microinsects from carpets or hard wearing textiles and fabrics, e.g.,
upholstery,
rugs, curtains.
The composition
The compositions of the present invention are formulated as liquid
compositions.
Preferred compositions herein are aqueous compositions and therefore,
preferably comprise water more preferably in an amount of from 60% to 98%,
even more preferably of from 80% to 97% and most preferably 85% to 97% by
weight of the total composition.
The pH of the liquid compositions according to the present invention may
typically be from 1 to 14. in a preferred embodiment, the recommended pH range
is from 1 to 10, preferably from pH 2 to 8, more preferably from pH 3 to 7,
even
more preferably from pH 4.5 to 7 and most preferably from 3.5 to 6.5. Indeed,
it
has been surprisingly found that cleaning performance is further improved at
these preferred pH ranges. Also these preferred pH ranges contribute to the
stability of hydrogen peroxide, when present. Accordingly, the compositions
herein may further comprise an acid or base to adjust pH as appropriate.
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Preferred acids herein are organic or inorganic acids or mixtures thereof.
Preferred organic acids are acetic acid, or citric acid or a mixture thereof.
Preferred inorganic acids are sulfuric acid or phosphoric acid or a mixture
thereof. A particularly preferred acid to be used herein is an inorganic acid
and
most preferred is sulfuric acid.
Typical levels of such acids, when present, are of from 0.01 % to 1.0%,
preferably
from 0.05% to 0.8% and more preferably from 0.1 % to 0.5% by weight of the
total composition.
The bases to be used herein can be organic or inorganic bases. Suitable bases
for use herein are the caustic alkalis, such as sodium hydroxide, potassium
hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such, as
sodium andlor potassium oxide or mixtures thereof. A preferred base is a
caustic
alkali, more preferably sodium hydroxide andlor potassium hydroxide.
Other suitable bases include ammonia, ammonium carbonate and hydrogen
carbonate.
Typical levels of such bases, when present, are of from 0.01 % to 1.0%,
preferably from 0.05% to 0.8% and more preferably from 0.1 % to 0.5% by weight
of the total composition.
Poly lvin~ methyl ether / malefic acid) copolymer
As an essential ingredient the compositions according to the present invention
comprise a poly (vinyl methyl ether l malefic acid) copolymer.
The liquid compositions herein may comprise from 0.001 % to 10%, preferably
from 0.01 % to 5%, more preferably from 0.05% to 2% and most preferably 0.1
to 1 % by weight of the total composition of poly (vinyl methyl ether /
malefic acid)
copolymer.
Suitable poly (vinyl methyl ether / malefic acid) copolymers are according to
the
general formula
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COOH
~n
OCH3 COOH
wherein n (degree of polymerisation} is an integer of from 50 to 1600,
preferably
from 100 to 800, and more preferably from 200 to 400.
Accordingly, suitable poly (vinyl methyl ether I malefic acid) copolymers for
use
herein have an average molecular weight of from 1'000 to 10'000'000,
preferably
10'000 to 1'000'000, more preferably from 10'000 to 500'000, and most
preferably from 50'000 to 100'000.
Suitable poly (vinyl methyl ether I malefic acid) copolymers are commercially
available, for instance, from ISP Corporation, New York, NY and Montreal,
Canada under the product names Gantrez AN Copolymer~ {AN-119 copolymer,
average molecular weight of 20'000; AN-139 copolymer, average molecular
weight of 41'000; AN-149 copolymer, average molecular weight of 50'000; AN-
169 copolymer, average molecular weight of 67'000; AN-179 copolymer, average
molecular weight of 80'000), Gantrez S~ (Gantrez S97~, average molecular
weight of 70'000), and Gantrez ES~ (ES-225, ES-335, ES-425, ES-435),
Gantrez V~ (V-215, V-225, V-425).
Preferably the poly (vinyl methyl ether / malefic acid) copolymers are either
crosslinked or not crosslinked, i:e., linear. More preferably the poly (vinyl
methyl
ether I malefic acid) copolymers are not crosslinked.
It has now been found that when poly (vinyl methyl ether / malefic acid)
copolymers, as described herein are added into liquid compositions, a film,
i.e., a
layer of these polymers, is left on the carpet fibers treated with said
composition.
The film reduces adhesion of soils onto said carpet fibers treated with the
composition according to the present invention and/or facilitate removal of
soils
subsequently deposited thereon. Thus, less effort (e.g., less vacuum cleaning
andlor less chemical action) is required to remove the soils in the next
cleaning
operation ("carpet anti-resoiling performance/ benefit"), as compared to the
cleaning of a similarly soiled carpet which has been first treated with the
same
composition but wherein an anti-resoiling agent is absent.
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Furthermore, It has been found that the presence of the poly (vinyl methyl
ether
malefic acid) copolymers, in the compositions herein further contributes to
the
overall cleaning performance ("carpet cleaning benefit") of the compositions
herein.
Indeed, it has been observed that the poly (vinyl methyl ether / malefic acid)
copolymers are capable of complexing or even encapsulating soil particles on a
treated carpet and thereby form solid and glassy residues with said soil
particles
upon drying of the composition as described herein. More particularly, more
than
90%, preferably more than 95% of the residues left onto the carpet are solid
and
glassy. By 'glassy' it is meant that the residues are non-sticky, i.e., they
do not
stick to the carpet fibers andlor each other. This results in a process of
cleaning
carpets whereby the solid and glassy residues left onto the carpets are
removed
more easily as opposed to residues being sticky, and thus difficult to remove
(e.g., by vacuum cleaning said carpets). The presence of the poly (vinyl
methyl
ether / malefic acid) copolymers reduces or even prevents the formation of
tacky
residues on the surface of the carpet upon drying, as compared to the same
compositions but without the poly (vinyl methyl ether / malefic acid)
copolymers.
Additionally, by almost completely removing the residues the present invention
reduces or even prevents soil re-deposition on the carpet.
The compositions employed in the process of cleaning carpets according to the
present invention provide excellent cleaning performance on various types of
soils including diffuse soils (e.g., particulate andlor greasy soils) that
tend to
accumulate in the so called "high traffic areas" but also in delivering good
cleaning performance on other types of stains or soils, i.e., enzymatic stains
like
blood.
By "high traffic areas" it is meant herein areas with an intensive use of the
carpets in such areas as for example near doors.
By "particulate stains" it is meant herein any soils or stains of particulate
nature
that can be found on any carpet, e.g. clay, dirt, dust, mud, concrete and the
like.
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By "greasyloily stains" it is meant herein any soils or stains of greasyloily
nature
that can be found on any carpet, e:g., make-up, lipstick, dirty motor oil and
mineral oil, greasy food like mayonnaise and spaghetti sauce.
By "enzymatic stains" it is meant herein any soils or stains of enzymatic
nature
that can be found on any carpet, e.g., grass.
The cleaning performance of a given composition on a soiled carpet may be
evaluated by the following test method : A liquid composition according to the
present invention is first applied, preferably sprayed, onto the stained
portion of a
carpet, left to act thereon from 1 to 60 minutes, preferably 30 minutes, after
which the carpet is vacuum cleaned using any commercially available vacuum
cleaners like for instance a standard Hoover~ 1300W vacuuming machine. The
soils used in this test may be particulate stains, greasyloily stains or
enzymatic
stain as described above. The cleaning performance may be evaluated by visual
using panel score units to rate the cleaning performance.
The anti-resoiling performance of a give composition on a soiled carpet may be
evaluated by the following test method : A liquid composition according to the
present invention is first applied, preferably sprayed, onto the carpet,
preferably
the stained portion of said carpet, left to act thereon from 1 to 60 minutes,
preferably 30 minutes, after which the carpet is vacuum cleaned using any
commercially available vacuum cleaners like for instance a standard Hoover~
1300W vacuuming machine. The carpet is left in a 'high traffic area' for a
period
of time of from 1 hour to several weeks, preferably several days. The anti
resoiling performance may be evaluated by visual grading using panel score
units to rate the anti resoifing performance.
Optional ingredients
Peroxvaen bleach
As an optional but highly preferred ingredient the compositions according to
the
present invention may comprise a peroxygen bleach.
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Suitable peroxygen bleaches to be used herein are selected from the group
consisting of : hydrogen peroxide; water soluble sources of hydrogen peroxide;
organic or inorganic peracids; hydroperoxides; diacyl peroxides; and mixtures
thereof.
As used herein a hydrogen peroxide source refers to any compound that
produces perhydroxyl ions when said compound is in contact with water.
Suitable
water-soluble sources of hydrogen peroxide for use herein are selected from
the
group consisting of percarbonates, perborates and persilicates and mixtures
thereof.
Suitable diacyl peroxides for use herein are selected from the group
consisting of
aliphatic, aromatic and aliphatic-aromatic diacyl peroxides, and mixtures
thereof.
Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide,
didecanoyl peroxide, dimyristoyl peroxide, or mixtures thereof. A suitable
aromatic diacyi peroxide for use herein is for example benzoyl peroxide. A
suitable aliphatic-aromatic diacyl peroxide for use herein is for example
lauroyl
benzoyl peroxide. Such diacyl peroxides have the advantage to be particularly
safe to carpets and carpet dyes while delivering excellent bleaching
performance.
Suitable organic or inorganic peracids for use herein are selected from the
group
consisting of : persulphates such as monopersulfate; peroxyacids such as
diperoxydodecandioic acid (DPDA); magnesium perphthalic acid; perlauric acid;
perbenzoic and alkylperbenzoic acids; and mixtures thereof.
Suitable hydroperoxides for use herein are selected from the group consisting
of
tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-
hydroperoxide, di-isopropylbenzene-monohydroperoxide, tert-amyl hydroperoxide
and 2,5-dimethyl-hexane-2,5-dihydroperoxide and mixtures thereof. Such
hydroperoxides have the advantage to be particularly safe to carpets and
carpet
dyes while delivering excellent bleaching performance.
Preferred peroxygen bleaches herein are selected from the group consisting of
hydrogen peroxide; water soluble sources of hydrogen peroxide; organic or
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inorganic peracids; hydroperoxides; and diacyl peroxides; and mixtures
thereof.
More preferred peroxygen bleaches herein are selected from the group
consisting of hydrogen peroxide, water soluble sources of hydrogen peroxide
and
diacyl peroxides and mixtures thereof. Even more preferred peroxygen bleaches
herein are selected from the group consisting of hydrogen peroxide, water
soluble sources of hydrogen peroxide, aliphatic diacyl peroxides, aromatic
diacyl
peroxides and aliphatic-aromatic diacyl peroxides and mixtures thereof. Most
preferred peroxygen bleaches herein are hydrogen peroxide, water soluble
sources of hydrogen peroxide or mixtures thereof.
Typically, the liquid compositions herein comprise from 0.01 % to 20%,
preferably
from 0.5 % to 10%, and more preferably from 1 % to 7% by weight of the total
composition of a peroxygen bleach, or mixtures thereof.
The presence of a peroxygen bleach in preferred compositions employed in the
process of cleaning carpets according to the present invention contributes to
the
excellent cleaning and sanitizing performance on various types of soils
including
on spot stains like bleachable stains (e.g., coffee, beverage, food) of the
compositions of the present invention.
By "bleachable stains" it is meant herein any soils or stains containing
ingredients
sensitive to bleach that can be found on any carpet, e.g., coffee or tea.
Further anti-resoiling agent
The compositions as disclosed herein may comprise as a highly preferred
optional ingredient a further anti-resoiling agent on top of the poly {vinyl
methyl
ether / malefic acid) copolymers.
Suitable further anti-resoiling agents include anti-resoiling polymers.
Suitable anti-resoiling polymers include soil suspending polyamine polymers.
Any
soil suspending polyamine polymer known to those skilled in the art may also
be
used herein. Particularly suitable polyamine polymers for use herein are
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alkoxylated polyamines. Such materials can conveniently be represented as
molecules of the empirical structures with repeating units
[N R] n Amine form
(alkoxy)y
and
R1
I
[N+ R] n nX- Quaternized form
I
(alkoxy)y
wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C~-
C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is
from 2 to 30, most preferably from 7 to 20; n is an integer of at least 2,
preferably
from 2 to 40, most preferably from 2 to 5; and X- is an anion such as halide
or
methylsulfate, resulting from the quaternization reaction.
The most highly preferred pofyamines for use herein are the so-called
ethoxylated polyethylene amines, i.e., the polymerized reaction product of
ethylene oxide with ethyleneimine, having the general formula
(Et0)y [N CH~CH2 1 n N (Et0)y
I
(Et0)y (Et0)y
wherein y is from 2 to 50, preferably from 5 to 30, and n is from 1 to 40,
preferably from 2 to 40. Particularly preferred for use herein is an
ethoxylated
polyethylene amine, in particular an ethoxylated polyethylene amine wherein
n=2
and y=20, and an ethoxylated polyethylene amine wherein n=40 and y=7.
Suitable ethoxylated polyethylene amines are commercially available from
Nippon Shokubai CO., LTD under the product names ESP-0620A~ (ethoxylated
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polyethylene amine wherein n=2 and y=20) or from BASF under the product
names ES-8165 and from BASF under the product name LUTENSIT K - 187/50
~ (ethoxylated polyethylene amine wherein n=40 and y=7)
Suitable anti-resoiling polymers also include polyamine N-oxide polymers.
Suitable polyamine N-oxide polymers for use herein are according to the
following formula : R-Ax-P; containing at least one N-oxide group {N-O group);
wherein : P is a poiymerizable unit to which an N-O group can be attached
and/or
the N-O group can form part of the polymerizable unit;
A is one of the following structures:
-NC- -CO- -C- -N- -O- -S- .
xis0or1;
and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or
alicyclic
group or any combination thereof to which the N-O group can be attached to R
or
the nitrogen of the N-O group is part of R.
By "N-O group" it is meant one of the following general structures:
Q
(Rt)X i -fR2)y; =N-(R~lx
(R3lz
wherein R1, R2, Rg are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can
be attached or form part of any of the aforementioned groups.
Any polymerizable unit P can be used as long as the amine oxide polymer formed
is water-soluble and provides the carpet cleaning composition with carpet
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cleaning andlor carpet anti-resoiling benefits. Preferred polymerizable unit P
are
vinyl, alkylenes, esters, ethers, amides, imides, acrylates and mixtures
thereof. A
more preferred polymerizable unit P is vinyl.
Preferred polyamine N-oxide polymers are those wherein R is a heterocyclic
group such as pyridine, pyrrole, imidazole, or a derivative thereof, to which
the
nitrogen of the N-O group can be attached or the N-O group is part of these
groups. Most preferred polyamine N-oxide polymers are those wherein R is a
pyridine.
The polyamine N-oxide polymer can be obtained in almost any degree of
polymerization. Typically, the average molecular weight is within the range of
1,000 to 100,000; more preferred 5,000 to 100,000; most preferred 5,000 to
25,000.
Suitable polyamine N-oxide polymers are polyvinyl pyridine-N-oxide polymers
wherein : the polymerizable unit P is vinyl; x=0; and R is pyridine wherein
the
nitrogen of the N-O group is part of.
Suitable poly vinyl pyridine-N-oxide polymers are commercially available from
Hoechst under the trade name of Hoe S 4268~, and from Reilly Industries Inc.
under the trade name of PVNO.
Furthermore, suitable anti-resoiling polymers include N-vinyl polymer.
Suitable N-vinyl polymers include polyvinyl pyrrolidone polymers, co-polymers
of
N-vinylpyrrolidone and N-vinylimidazole, co-polymers of N-vinylpyrrolidone and
acrylic acid, and mixtures thereof.
Suitable co-polymers of N-vinylpyrrolidone and N-vinylimidazole polymers
(referred to as a class as "PVPVI") are according to the formula
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18
i
C-C C-CHZ
N N
-N
m
in which n is between 50 and 500 and preferably between 80 and 200 and m is
between 50 and 500 and preferably between 80 and 200.
Preferably the PVPVI has an average molecular weight range from 1,000 to
100,000, more preferably from 5,000 to 100,000, and most preferably from 5,000
to 20,000. (The average molecular weight range is determined by light
scattering
as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of
Polymer Characterization", the disclosures of which are incorporated herein by
reference.)
The PVPVI co-polymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most
preferably from 0.6:1 to 0.4:1. These co-polymers can be either linear or
branched.
Suitable co-polymers of N-vinyipyrrolidone and N-vinyfimidazole are
commercially
available from BASF, under the trade name of Sokalan~ PG55.
Suitable polyvinylpyrrolidones ("PVP") for use herein are homopolymers of N-
vinylpyrrolidone having the following repeating monomer:
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19
-'CH2
,N~
H2 ~ ~-O
H2 C~ CH2
Preferred vinylpyrrolidone homopolymers for use herein have an average
molecular weight of from 1,000 to 100,000, preferably from 5,000 to 100,000,
and more preferably from 5,000 to 20,000.
Suitable vinylpyrrolidone homopoiymers are commercially available from BASF
under the trade names Luviskol~ K15 (viscosity molecular weight of 10,000),
Luviskol~ K25 (viscosity molecular weight of 24,000), Luviskol~ K30 (viscosity
molecular weight of 40,000), and other vinylpyrrolidone homopolymers known to
persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-
256,696).
Suitable co-polymers of N-vinylpyrrolidone and acrylic acid (referred to as a
class
as "PV/AA") are according to the formula
CH2 ~ CH2
N O ~C
O OH
m
n
in which n is between 50 and 1000 and preferably between 100 and 200 and m
is between 150 and 3000 and preferably between 300 and 600.
Preferably the PV/AA have an average molecular weight range from 1,000 to
100,000, more preferably from 5,000 to 100,000, and most preferably from 5,000
to 25,000.
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Suitable co-polymers of N-vinylpyrrolidone and acrylic acid are commercially
available from BASF under the trade name Sokalan~ PG 310.
Preferred N-vinyl polymers are polyvinyl pyrrolidone polymers, co-polymers of
N-
vinylpyrrolidone and N-vinylimidazole, co-polymers of N-vinylpyrrolidone and
acrylic acid, and mixtures thereof, even more preferred are polyvinyl
pyrrolidone
polymers.
Suitable anti-resoiling polymers also include soil suspending polycarboxylate
polymers.
Any soil suspending polycarboxylate polymer known to those skilled in the art
can be used according to the present invention such as homo- or co-polymeric
polycarboxylic acids or their salts including polyacrylates and copolymers of
malefic anhydride or/and acrylic acid and the like. Indeed, such soil
suspending
polycarboxylate polymers can be prepared by polymerizing or copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated
monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric polycarboxylates herein
of monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether, styrene, ethylene, etc. is suitable provided that such segments do not
constitute more than 40% by weight.
Particularly suitable-polymeric polycarboxylates to be used herein can be
derived
from acrylic acid. Such acrylic acid-based polymers which are useful herein
are
the water-soluble salts of polymerized acrylic acid. The average molecular
weight
of such polymers in the acid form preferably ranges from 2,000 to 10,000, more
preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-
soluble salts of such acrylic acid polymers can include, for example, the
alkali
metal, ammonium and substituted ammonium salts. Soluble polymers of this type
are known materials. Use of polyacrylates of this type in detergent
compositions
has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March
7, 1967.
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21
Acrylic/maleic-based copolymers may also be used as a preferred soil
suspending poiycarboxylic polymer. Such materials include the water-soluble
salts of copolymers of acrylic acid and malefic acid. The average molecular
weight of such copolymers in the acid form preferably ranges from 2,000 to
9 00,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to
65,000. The ratio of acrylate to maleate segments in such copolymers will
generally range from 30:1 to 1:1, more preferably from 10:1 to 2:1. Water-
soluble
salts of such acrylic acid/maleic acid copolymers can include, for example,
the
alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/rnaleate copolymers of this type are known materials which are
described in European Patent Application No. 66915, published December 15,
1982. Particularly preferred is a copolymer of malefic / acrylic acid with an
average molecular weight of 70,000. Such copolymers are commercially
available from BASF under the trade name SOKAI_AN~ CPS.
Other suitable anti-resoiling polymers include those anti-resoiling polymers
having: (a) one or more nonionic hydrophile components consisting essentially
of
(i) polyoxyethylene segments with a degree of polymerization of at least 2, or
{ii)
oxypropylene or polyoxypropylene segments with a degree of polymerization of
from 2 to 10, wherein said hydrophile segment does not encompass any
oxypropylene unit unless it is bonded to adjacent moieties at each end by
ether
linkages, or {iii) a mixture of oxyalkylene units comprising oxyethylene and
from 1
to about 30 oxypropylene units wherein said mixture contains a sufficient
amount
of oxyethylene units such that the hydrophile component has hydrophilicity
great
enough to increase the hydrophilicity of conventional polyester synthetic
fiber
surfaces upon deposit of the soil release agent on such surface, said
hydrophile
segments preferably comprising at feast about 25% oxyethylene units and more
preferably, especially for such components having about 20 to 30 oxypropylene
units, at least about 50% oxyethylene units; or (b) one or more hydrophobe
components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if
said hydrophobe components also comprise oxyethylene terephthalate, the ratio
of oxyethylene terephthalate: Cg oxyalkylene terephthalate units is about 2:1
or
lower, (ii) C4-Cg alkyiene or oxy C4-C6 alkylene segments, or mixtures
therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a
degree of
polymerization of at least 2, or {iv) C1-C4 alkyl ether or C4 hydroxyalkyi
ether
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22
substituents, or mixtures therein, wherein said substituents are present in
the
form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or
mixtures therein, and such cellulose derivatives are amphiphiiic, whereby they
have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether
units to
deposit upon conventional polyester synthetic fiber surfaces and retain a
sufficient level of hydroxyls, once adhered to such conventional synthetic
fiber
surface, to increase fiber surface hydrophilicity, or a combination of (a) and
(b).
Typically, the pofyoxyethylene segments of (a)(i) will have a degree of
polymerization of from about 1 to about 200, although higher levels can be
used,
preferably from 3 to about 150, more preferably from 6 to about 100. Suitable
oxy
C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps
of
polymeric soil release agents such as M03S(CH2)nOCH2CH20-, where M is
sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink.
Anti-resoiling polymers useful in the present invention also include
cellulosic
derivatives such as hydroxyether cellulosic polymers, co-polymeric blocks of
ethylene terephthalate or propylene terephthalate with polyethylene oxide or
polypropylene oxide terephthalate, and the like. Such anti-resoiling polymers
are
commercially available and include hydroxyethers of cellulose such as
METHOCEL~ (Dow). Cellulosic anti-resoiling polymers for use herein also
include those selected from the group consisting of C1-C4 alkyl and C4
hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to
Nicol, et al.
Anti-resoi(ing polymers characterised by polyvinyl ester) hydrophobe segments
include graft co-polymers of polyvinyl ester), e.g., C1-C6 vinyl esters,
preferably
poly{vinyl acetate) grafted onto polyalkylene oxide backbones, such as
polyethylene oxide backbones. See European Patent Application 0 219 048,
published April 22, 1987 by Kud, et al. Commercially available anti-resoiling
polymers of this kind include the SOKALAN~ type of material, e.g., SOKALAN
HP-22~, available from BASF.
One type of preferred anti-resoiling polymer is a co-polymer having random
blocks of ethylene terephthalate and polyethylene oxide {PEO) terephthalate.
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23
The molecular weight of this anti-resoiling polymer is in the range of from
about
25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25,
1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred anti-resoiling polymers is a polyester with repeat units of
ethylene terephthalate units which contains 10-15% by weight of ethylene
terephthalate units together with 90-80% by weight of polyoxyethylene
terephthalate units, derived from a polyoxyethylene glycol of average
molecular
weight 300-5,000. Examples of this polymer include the commercially available
material ZELCON 5126~ (from Dupont) and MILEASE T~ (from ICI). See also
U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
Another preferred anti-resoiling polymer is a sulfonated product of a
substantially
linear ester oligomer comprised of an oligomeric ester backbone of
terephthaloyl
and oxyalkyleneoxy repeat units and terminal moieties covafently attached to
the
backbone. These anti-resoiling polymers are fully described in U.S. Patent
4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other
suitable anti-resoiiing polymers include the terephthalate polyesters of U.S.
Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-
capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink, and the block polyester oiigomeric compounds of U.S. Patent
4,702,857, issued October 27, 7987 to Gosselink.
Preferred anti-resoifing polymers also include the soil release agents of U.S.
Patent 4,877,896, issued October 31, 1989 to Maldonado et af., which discloses
anionic, especially sulfoaroyl, end-capped terephthalate esters.
Still another preferred anti-resoiling agent is an oligomer with repeat units
of
terephthaloyl units, sulfoisoterephthaloyl units, oxyethyieneoxy and oxy-1,2-
propylene units. The repeat units form the backbone of the oligomer and are
preferably terminated with modified isethionate end-caps. A particularly
preferred
anti-resoiling agent of this type comprises about one sulfoisophthaloyl unit,
5
terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio
of
from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-
hydroxyethoxy~ethanesulfonate. Said anti-resoiling agent also comprises from
about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing
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24 .
stabilizer, preferably selected from the group consisting of xylene sulfonate,
cumene sulfonate, toluene sulfonate, and mixtures thereof. See U.S. Pat. No.
5,415,807, issued May 16, 1995, to Gossefink et al.
The liquid compositions may comprise from 0.01 % to 10%, preferably from
0.01 % to 5%, and more preferably from 0.05% to 2% by weight of the total
composition of a further anti-resoiling agent.
A preferred further anti-resoiling agent is an anti-resoiling polymer. A more
preferred further anti-resoiling agent is a soil suspending polyamine polymer.
An
even more preferred further anti-resoiling agent is an alkoxyiated polyamine
polymer. The most preferred further anti-resoiling agent useful in the
compositions herein are selected from the group consisting of : an ethoxylated
polyethylene amine according to the formula as described above wherein n=2
and y=20, and an ethoxylated polyethylene amine according to the formula as
described herein wherein n=40 and y=7.
Other optional in4redients
The compositions herein may further comprise conventional carpet cleaning
ingredients. Preferably, the compositions herein may comprise a number of
additionai compounds such as volatile organic compounds, surfactants,
stabilising agents, chelating agents, builder systems, radical scavengers,
perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents,
bleach activators and other minors.
In a preferred embodiment, the compositions herein may further comprise a
number of additional compounds such as stabilising agents, chelating agents,
builder systems, radical scavengers, perfumes, dyes, suds suppressing agents,
enzymes, photobleaching agents, bleach activators and other minors.
Volatile or4anic compounds
As an optional but highly preferred ingredient the compositions according to
the
present invention may comprise a volatile organic compound (VOC) or a mixture
thereof.
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Typically, the compositions herein may comprise up to 90%, preferably from
0.1 % to 20%, more preferably from 0.5% to 10% and most preferably from 1 % to
5% by weight of the total composition of a volatile organic compound or a
mixture
thereof.
Suitable volatile organic compounds for use herein are selected from the group
consisting of : an aliphatic andlor aromatic alcohol; a glycol ether and/or a
derivative thereof; a polyol; and a mixture thereof.
Suitable aromatic alcohols to be used herein are according to the formula R1-
OH
wherein R1 is an alkyl substituted or non-alkyl substituted aryl group of from
1 to
20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10. A
suitable aromatic alcohol to be used herein is benzyl alcohol.
Suitable aliphatic alcohols to be used herein are according to the formula R2-
OH
wherein R2 is a linear or branched saturated or unsaturated hydrocarbon chain
of from 1 to 20 carbon atoms, preferably from 1 to 10 and more preferably from
2
to 6. Highly preferred herein are aliphatic alcohols with 2 to 4 carbon atoms
and
most preferably 4 carbon atoms, or mixtures thereof. Suitable aliphatic
alcohois
to be used herein include linear alcohol like 2-octanol, decanol, isopropyl
alcohol,
propyl alcohol, ethanol andlor methanol. Highly preferred .herein are ethanol,
isopropyl alcohol or a mixture thereof.
Ethanol may be commercially available from Eridania Italia under its chemical
name.
Isopropanol may be commercially available from MerckJBDH Italia under its
chemical name.
Suitable glycol ethers andlor derivatives thereof to be used herein include
monogiycol ethers and/or derivatives thereof, polygfycol ethers and/or
derivatives
thereof and mixtures thereof.
Suitable monoglycol ethers and derivatives thereof to be used herein include n-
buthoxypropanol (n-BP), water-soluble CELLOSOLVE~ solvents or mixtures
thereof. Preferred Cellosolve~ solvents include propoxy ethyl acetate salt
(i.e.,
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26
Propyl Cellosoive acetate salt~), ethanol-2-butoxy phosphate salt (i.e., Butyl
Cellosolve phosphate salt~), 2-(Hexyloxy)ethanol (i.e., 2-hexyl Cellosolve~),
2-
ethoxy ethanol (i.e., 2-ethyl Cellosolve~), 2-butoxyethanol (i.e., 2-buthyl
Cellosolve~) or mixtures thereof.
Suitable polyglycol ethers and derivatives thereof to be used herein include n-
butoxypropoxypropanol (n-BPP), butyl triglycol ether (BTGE), butyl diglycol
ether
(BDGE), water-soluble CARBITOL~ solvents or mixtures thereof.
Preferred water-soluble CARBITOL~ solvents are compounds of the 2-(2-
alkoxyethoxy)ethanol class, 2-(2-alkoxyethoxy)propanol class andlor 2-(2-
alkoxyethoxy)butanol class wherein the alkoxy group is derived from ethyl,
propyl
or butyl. A preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also
known as butyl carbitol~.
Preferred glycol ethers and/or derivatives thereof are 2-ethoxyethanol, 2-
butoxyethanol, n-butoxypropoxypropanol, butyl carbitol~ or mixtures thereof.
Suitable polyol solvents to be used herein are the polyols having at least 2
hydroxyl groups (-OH) like diols. Suitable diols to be used herein include 2-
ethyl-
1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, methyl-2,4 pentanediol or
mixture thereof.
The volatile organic compounds, when present, further contribute to the
excellent
overall cleaning performance of the present invention. Additionally, their
addition
in the compositions herein also enhances the sanitising properties of the
compositions.
Surfactants
Preferred compositions according to the present invention typically comprise a
surfactant or a mixture thereof.
Typically, the compositions herein may comprise up to 50%, preferably from
0.1 % to 20%, more preferably from 0.5% to 10% and most preferably from 1 % to
5% by weight of the total composition of a surfactant.
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27
Such surfactants may be selected from those well known in the art including
anionic, nonionic, zwitterionic, amphoteric and cationic surfactants and
mixtures
thereof.
Particularly suitable surfactants to be used herein are anionic surfactants.
Said
anionic surfactants are preferred herein as they further contribute to the
outstanding stain removal performance of the compositions of the present
invention on various types of stains. Moreover they do not stick on carpet,
thereby reducing resoiling.
Suitable anionic surfactants include sarcosinate surfactants, alkyl sulfate
surfactants, alkyl sulphonate surfactants, alkyl glycerol sulfate surfactants
and
alkyl glycerol sulphonate surfactants.
Suitable sarcosinate surfactants to be used herein include acyl sarcosinate or
mixtures thereof, in its acid and/or salt form, preferably long chain acyl
sarcosinates having the following formula:
O
OM
R
CH3 O
wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of
from 11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms.
Preferred
M are hydrogen and alkali metal salts, especially sodium and potassium. Said
acyl sarcosinate surfactants are derived from natural fatty acids and the
amino-
acid sarcosine (N-methyl glycine). They are suitable to be used as aqueous
solution of their salt or in their acidic form as powder. Being derivatives of
natural
fatty acids, said acyl sarcosinates are rapidly and completely biodegradable
and
have good skin compatibility.
Accordingly, particularly preferred long chain acyl sarcosinates to be used
herein
include C12 acyl sarcosinate, i.e., an acyl sarcosinate according to the above
formula wherein M is hydrogen and R is an alkyl group of 11 carbon atom,
sodium N-lauroyl sarcosinate, i.e., an acyl sarcosinate according to the above
formula wherein M is sodium and R is an alkyl group of 11 carbon atom, and C14
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28
aryl sarcosinate (i.e., an aryl sarcosinate according to the above formula
wherein
M is hydrogen and R is an alkyl group of 13 carbon atoms). , sodium N-Iauroyl
sarcosinate is commercially available, for example, as Hamposyl L-30~ supplied
by Hampshire or Crodasinic LS30~ supplied by Croda. C14 aryl sarcosinate is
commercially available, for example, as Hamposyl M-30~ supplied by Hampshire
or Crodasinic MS30~ supplied by Croda.
Suitable alkyl sulphonates for use herein include water-soluble salts or acids
of
the formula RS03M wherein R is a Cg-C20 linear or branched, saturated or
unsaturated alkyl group, preferably a Cg-C1 g alkyl group and more preferably
a
C10-C16 alkyl group, and M is H or a ration, e.g., an alkali metal ration
(e.g.,
sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.,
methyl-, dimethyl-, and trimethyl ammonium rations and quaternary ammonium
rations, such as tetramethyl-ammonium and dimethyl piperdinium rations and
quaternary ammonium rations derived from alkylamines such as ethyfamine,
diethylamine, triethylamine, and mixtures thereof, and the like).
An example of a C14-C16 alkyl sulphonate is Hostapur~ SAS available from
Hoechst.
Suitable alkyl sulphate surfactants for use herein are according to the
formula
R1 S04M wherein R1 represents a hydrocarbon group selected from the group
consisting of straight or branched alkyl radicals containing from 6 to 20,
preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl
radicals containing from 6 to 18 carbon atoms in the alkyl group. M is H or a
ration, e.g., an alkali metal ration (e.g., sodium, potassium, lithium,
calcium,
magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-,
dimethyl-, and trimethyl ammonium rations and quaternary ammonium rations,
such as tetramethyl-ammonium and dimethyl piperdinium rations and quaternary
ammonium rations derived from alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures thereof, and the like).
By "linear alkyl sulphate or sulphonate" it is meant herein a non-substituted
alkyl
sulphate or sulphonate wherein the alkyl chain comprises from 6 to 20 carbon
atoms, preferably from 8 to 18 carbon atoms, and more preferably from 10 to 16
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carbon atoms, and wherein this alkyl chain is sulphated or sulphonated at one
terminus.
By "branched sulphonate or sulphate", it is meant herein an alkyl chain having
from 6 to 20 total carbon atoms, preferably from 8 to 18 total carbon atoms,
and
more preferably from 10 to 16 total carbon atoms, wherein the main alkyl chain
is
substituted by at least another alkyl chain, and wherein the alkyl chain is
sulphated or sulphonated at one terminus.
Particularly preferred branched alkyl sulphates to be used herein are those
containing from 10 to 14 total carbon atoms like Isalchem 123 AS~. Isalchem
123 AS~ commercially available from Enichem is a C12-13 surfactant which is
94% branched. This material can be described as CH3-(CH2}~,-
CH{CH20S03Na~(CH2)n-CH3 where n+m=8-9. Also preferred alkyl sulphates
are the alkyl sulphates where the alkyl chain comprises a total of 12 carbon
atoms, i.e., sodium 2-butyl octyl sulphate. Such alkyl sulphate is
commercially
available from Condea under the trade name lsofol~ 12S. Particularly suitable
liner alkyl sulphonates include C12-C16 paraffin sulphonate like Hostapur~ SAS
commercially available from Hoechst.
Suitable nonionic surfactants include amine oxide surfactants. Suitable amine
oxide surfactants are according to the formula R1 R2R3N0, wherein each of R1,
R2 and R3 is independently a saturated substituted or unsubstituted, linear or
branched alkyl groups of from 1 to 30 carbon atoms, preferably of from 1 to 20
carbon atoms, and mixtures thereof.
Particularly preferred amine oxide surfactants to be used according to the
present invention are amine oxide surfactants having the following formula
R1 R2R3N0 wherein R1 is a saturated linear or branched alkyl group of from 1
to
30 carbon atoms, preferably of from 6 to 20 carbon atoms, more preferably of
from 6 to 16 carbon atoms, and wherein R2 and R3 are independently
substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4
carbon atoms, preferably of from 1 to 3 carbon atoms, and more preferably are
methyl groups. Preferred amine oxide surfactants used herein are pure-cut
amine oxide surfactants, i.e., a pure single amine oxide surfactant, e.g. Cg
N,N-
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dimethyl amine oxide, as opposed to mixtures of amine oxide surfactants of
different chain lengths
Suitable amine oxide surfactants for use herein are for instance pure cut Cg
amine oxide, pure cut C10 amine oxide, pure cut C14 amine oxide, natural blend
Cg-C10 amine oxides as well as natural blend C12-C1g amine oxides. Such
amine oxide surfactants may be commercially available from Hoechst or
Stephan.
Suitable nonionic surfactants for use herein also include any ethoxylated Cg-
C24
fatty alcohol nonionic surfactant, alkyl propoxylates and mixtures thereof,
fatty
acid Cg-C24 alkanolamides, Cg-C2p polyethyiglycol ethers, polyethylene glycol
with molecular weight 1000 to 80000 and glucose amides, alkyl pyrrofidones.
Suitable cationic surfactants for use herein include quaternary ammonium
compounds of the formula RlR2RgR4N+ where R1,R2 and R3 are methyl
groups, and R4 is a C12-15 alkyl group, or where R1 is an ethyl or hydroxy
ethyl
group, R2 and R3 are methyl groups and R4 is a C12-15 alkyl group.
Suitable zwitterionic surfactants are zwitterionic betaine surfactants.
Suitable
zwitterionic betaine surfactants for use herein contain both a cationic
hydrophilic
group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the
same molecule at a relatively wide range of pH's. The typical anionic
hydrophilic
groups are carboxylates and sulphonates, although other groups like sulfates,
phosphonates, and the like can be used. A generic formula for the zwitterionic
betaine surfactant to be used herein is
R1-N+~R2)~R3)R4X-
wherein R1 is a hydrophobic group; R2 is hydrogen, C1-Cg alkyl, hydroxy alkyl
or
other substituted C1-Cg alkyl group; Rg is C1-Cg alkyl, hydroxy alkyl or other
substituted C1-C6 alkyl group which can also be joined to R2 to form ring
structures with the N, or a C1-Cg sulphonate group; R4 is a moiety joining the
cationic nitrogen atom to the hydrophilic group and is typically an alkylene,
hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms;
and
X is the hydrophilic group, which is a carboxylate or sulphonate group.
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31
Preferred hydrophobic groups R1 are aliphatic or aromatic, saturated or
unsaturated, substituted or unsubstituted hydrocarbon chains that can contain
linking groups such as amido groups, ester groups. More preferred R1 is an
alkyl
group containing from 1 to 24, preferably from 8 to 18, and more preferably
from
to 16 carbon atoms. These simple alkyl groups are preferred for cost and
stability reasons. However, the hydrophobic group R1 can also be an amido
radical of the formula Ra-C(O)-NH-(C(Rb)2)m, wherein Ra is an aliphatic or
aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon
chain, preferably an alkyl group containing from 8 up to 20, preferably up to
18,
more preferably up to 1 fi carbon atoms, Rb is selected from the group
consisting
of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3,
more preferably 3, with no more than one hydroxy group in any (C(Rb)2) moiety.
Preferred R2 is hydrogen, or a C1-C3 alkyl and more preferably methyl.
Preferred R3 is C1-C4 sulphonate group, or a C1-C3 alkyl and more preferably
methyl. Preferred R4 is (CH2)n wherein n is an integer from 1 to 10,
preferably
from 1 to 6, more preferably is from 1 to 3.
Some common examples of betainelsulphobetaine are described in U.S. Pat.
Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
Examples of particularly suitable alkyldimethyl betaines include coconut-
dimethyl
betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-
dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl
dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl
dimethyl betaine. For example Coconut dimethyl betaine is commercially
available from Seppic under the trade name of Amonyl 265~. Lauryl betaine is
commercially available from Albright & Wilson under the trade name Empigen
BB/L~.
Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropyl
betaine or C1p-C14 fatty acylamidopropylene(hydropropyiene)sulfobetaine. For
example C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine is
commercially available from Sherex Company under the trade name "Varion
CAS~ sulfobetaine".
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32
A further example of betaine is Lauryl-immino-dipropionate commercially
available from Rhone-Poulenc under the trade name Mirataine H2C-HA~.
A preferred surfactant for use herein is an anionic surfactant or a
zwitterionic
surfactant or a mixture thereof, a more preferred surfactant is a sarcosinate
surfactant, an alkyl sulphonate surfactant, an alkyl sulphate surfactant, an
alkyl
glycerol sulphate surfactant, an alkyl glycerol sulphonate surfactant or a
zwitterionic betaine surfactant and mixtures thereof, an even more preferred
surfactant is a sarcosinate surfactant, an alkyl sufphonate surfactant, an
alkyl
sulphate surfactant, or a zwitterionic betaine surfactant and mixtures
thereof, and
the most preferred surfactant herein is an alkyl sarcosinate surfactant.
It has been found that poly (vinyl methyl ether / malefic acid) copolymers as
described herein can increase the activity of surfactants, preferably anionic
surfactants andlor zwitterionic surfactants, most preferably sarcosinate
surfactants, when present. Said increase in activity is thought to be due to
an
interaction of the poly (vinyl methyl ether I malefic acid) copolymer and a
surfactant, preferably an anionic surfactant and/or a zwitterionic surfactant,
most
preferably a sarcosinate surfactant. Said increase in activity further
contributes to
the overall cleaning performance of the compositions herein.
Stabilizing agents
The compositions of the present invention may further comprise a stabilizing
agent selected from the group consisting of hydroxy pyridine N-oxides or
derivatives thereof and mixtures thereof.
Suitable hydroxy pyridine N-oxides or derivatives thereof are according to the
following formula:
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wherein X is nitrogen, Y is one of the following groups oxygen, -CHO, -OH, -
(CH2)n-COOH, wherein n is an integer of from 0 to 20, preferably of from 0 to
10
and more preferably is 0, and wherein Y is preferably oxygen. Accordingly
particularly preferred hydroxy pyridine N-oxides or derivatives thereof to be
used
herein is 2-hydroxy pyridine N-oxide.
Hydroxy pyridine N-oxides or derivatives thereof may be commercially available
from Sigma.
Typically, the compositions herein may comprise up to 2%, preferably from
0.001 % to 1 % and more preferably from 0.001 % to 0.5% by weight of the total
composition of a hydroxy pyridine N-oxide or derivatives thereof or mixtures
thereof.
Chelating agents
The compositions of the present invention may further comprise a chelating
agent.
Suitable chelating agents are those known to those skilled in the art.
Particularly
suitable chelating agents include for examples phosphonate chelating agents,
polyfunctionally-substituted aromatic chelating agents, amino carboxylate
chelating agents, other chelating agents like ethylene diamine N,N'-
disuccinic
acid and mixtures thereof.
Typically, the compositions herein may comprise up to 4%, preferably from
0.001 % to 1 %, and more preferably from 0.001 % to 0.5% by weight of the
total
composition of a chetating agent.
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34
Suitable phosphonate chelating agents to be used herein may include ethydronic
acid, alkali metal ethane 1-hydroxy diphosphonates as well as amino
phosphonate compounds, including amino alkylene poly (alkylene phosphonate),
alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene
phosphonates,
ethylene diamine tetra methylene phosphonates, and diethylene triamine penta
methylene phosphonates. The phosphonate compounds may be present either
in their acid form or as salts of different cations on some or ail of their
acid
functionalities. Preferred phosphonate chelating agents to be used herein are
diethylene triamine yenta methylene phosphonates (DETPMP). Such
phosphonate chelating agents are commercially available from Monsanto under
the trade name DEQUEST~.
Polyfunctionally-substituted aromatic chelating agents may also be useful in
the
compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to
Connor et al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine
N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or
substitutes
ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic
acids, especially the (S,S) isomer, have been extensively described in US
patent
4, 704, 233, November 3, 1987. to Hartman and Perkins. Ethylenediamine N,N'-
disuccinic acid is, for instance, commercially available under the tradename
ssEDDS~ from Palmer Research Laboratories.
Suitable amino carboxylate chelating agents to be used herein include ethylene
diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine
pentaacetate (DTPA), N-hydroxyethyfethylenediamine triacetates, nitriiotri-
acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-
acetates,
ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine
di-acetic acid (MGpA), both in their acid form, or in their alkali metal,
ammonium,
and substituted ammonium salt forms. A particularly suitable amino carboxylate
to be used herein is diethylene triamine yenta acetic acid (DTPA).
Other suitable chelating agents to be used herein include salicylic acid or
derivatives thereof, or mixtures thereof according to the following formula:
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WO 00/26330 PCT/US99/22841
H
wherein X is carbon, Y is one of the following groups -CHO, -OH, -(CH2)n-
COOH, and preferably is -(CH2)n-COOH, and wherein n is an integer of from 0
to 20, preferably of from 0 to 10 and more preferably is 0. Salicylic acid and
derivatives thereof may be used herein either in their acid form or in their
salts
form as for example sodium salts.
Salicylic acid is particularly preferred herein and may be commercially
available
from Rhone Poulenc.
Bleach activators
In an embodiment of the present invention where the compositions herein
comprise a peroxygen bleach, preferably hydrogen peroxide, said compositions
may further comprise a bleach activator, as an optional ingredient.
By "bleach activator", it is meant herein a compound which reacts with the
peroxygen bleach, preferably hydrogen peroxide, to form a peracid. The peracid
thus formed constitutes the activated bleach.
Suitable bleach activators to be used herein include those belonging to the
class
of esters, amides, imides, or anhydrides. Examples of suitable compounds of
this
type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a
method for their formation into a grilled form is described in European
Published
Patent Application EP-A-62 523. Suitable examples of such compounds to be
used herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl
hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for
instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for
' instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOES). Also
suitable are N-acyl caprolactam selected from the group consisting of
substituted
or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl
caprolactam, hexanoyl caprofactam, decanoyl caprolactam, undecenoyl
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36
caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caproiactam,
butanoyl caprolactam pentanoyl caprolactam or mixtures thereof. A particular
family of bleach activators of interest was disclosed in EP 624 154, and
particularly preferred in that family is acetyl triethyl citrate (ATC). Acetyl
methyl
citrate has the advantage that it is environmentally friendly as it eventually
degrades into citric acid and alcohol. Furthermore, acetyl triethyl citrate
has a
good hydrolytical stability in the composition upon storage and it is an
efficient
bleach activator.
The compositions according to the present invention may comprise up to 30%,
preferably from 1 % to 20%, and more preferably from 2% to 10% by weight of
the total composition of a bleach activator.
Builders
The compositions according to the present invention may further comprise a
builder system. Any conventional builder system known in the art is suitable
for
use herein. Suitable builders for use herein include derivatives of succinic
acid of
the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl,
preferably C12_1g alkyl or alkenyl, or wherein R can be substituted with
hydroxyl,
sulpho sulphoxyl or sulphone substituents. Specific examples include lauryl
succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2-
tetradecenyl succinate. Succinate builders are preferably used in the form of
their
water-soluble salts, including sodium, potassium, ammonium and
alkanolammonium salts.
Other suitable builders are oxodisuccinates and mixtures of tartrate
monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Further suitable builders for use herein are fatty acid builders including
saturated
or unsaturated C10_1g fatty acids, as well as the corresponding soaps.
Preferred
saturated species have from 12 to 16 carbon atoms in the alkyl chain. The
preferred unsaturated fatty acid is oleic acid.
The compositions herein may comprise up to 10%, preferably from 1 % to 7% by
weight of the total composition of a builder system.
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Radical scavengers:
The compositions herein may comprise a radical scavenger as another optional
ingredient. Suitable radical scavengers for use herein include the well-known
substituted mono and di hydroxy benzenes and derivatives thereof, alkyl- and
aryl
carboxylates and mixtures thereof. Preferred radical scavengers for use herein
include di-tert-butyl hydroxy toluene (BHT), p-hydroxy-toluene, hydroquinone
(HQ),
di-tert-butyl hydroquinone (DTBHQ), mono-tert-butyl hydroquinone (MTBHQ), tert-
butyl-hydroxy anysole (BHA), p-hydroxy-anysol, benzoic acid, 2,5-dihydroxy
benzoic acid, 2,5-dihydroxyterephtalic acid, toluic acid, catechol, t-butyl
catechol,
4-allyl-catechol, 4-acetyl catechol, 2-methoxy-phenol, 2-ethoxy-phenol, 2-
rnethoxy-
4-(2-propenyl)phenol, 3,4-dihydroxy benzaidehyde, 2,3-dihydroxy benzaldehyde,
benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyi) butane, tert-butyl-
hydroxy-anyline, p-hydroxy anyGne as well as n-propyl-gallate. Highly
preferred for
use herein is di-tert-butyl hydroxy toluene, which is for example commercially
available from SHELL under the trade name IONOL CP~ and/or tert-butyl-hydroxy
anysole andlor propyl gallate. These radical scavengers further contribute to
the
stability of the compositions herein.
Typically, the compositions according to the present invention may comprise up
to
5%, preferably from 0.002% to 1.5% by weight and more preferably from 0.002%
to 0.5% by weight of the total composition of a radical scavenger.
Experimental data and Examples
The following Examples are meant to exemplify compositions used in a process
according to the present invention but are not necessarily used to limit or
otherwise define the scope of the present invention.
Data on the benefits associated with the compositions of the present invention
The following compositions were made by mixing the listed ingredients in the
listed proportions (weight % unless othenrvise specified). The compositions
were
then used in a process according to the present invention to clean a carpet.
Compositions 1 ll ill IV
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(weight %)
Hydrogen peroxide 4.0 4.0 4.0 4.0
Gantrez S97~ -- -- 0.3 0.4
ESP-0620A~ -- 0.5 0.2 0.1
Ethanol 3.0 3.0 3.0 3.0
Sarcosinate 3.0 3.0 3.0 3.0
BHT 0.01 0.01 0.01 0.01
Chelant* 0.2 0.2 0.2 0.2
Salicylic Acid 0.5 0.5 0.5 0.5
Water and minors Balance Balance Balance Balance
up to pH 6 6 6 6
Cleaning performance
Particulate stains 0 psu + 1 psu + 1.2 psu + 1.5
psu
Bleachable stains 0 psu + 0.9 psu + 1.2 psu + 1.4
psu
Greasy stains 0 psu + 1.1 psu + 1.2 psu + 1.6
psu
Anti-resoiling performance0 psu + 1 psu + 2 psu + 3 psu
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Compositions V VI
(weight %)
Hydrogen peroxide 4.0 4.0
Gantrez S97~ 0.4 0.5
E S P-0620A~ -- ---
PA 0.1 --
Ethanol ~ 3.0 3.0
Sarcosinate 3.0 3.0
BHT 0.01 0.01
Chelant* 0.2 0.2
Salicylic Acid 0.5 0.5
Water and minors Balance Balance
up to pH 6 6
Cleaning performance
Particulate stains + 1.3 psu + 1.3
psu
Bleachable stains + 1.5 psu + 1.2
psu
Greasy stains + 1.3 psu + 1.3
psu
Anti-resoiling performance + 3 psu + 3.5 psu
Gantrez S97~ is poly (vinyl methyl ether / malefic acid) copolymer
commercially
available from ISP Corporation.
ESP-0620A~ is ethoxylated polyethylene amine commercially available from
Nippon Shokubai CO., LTD.
Sarcosinate is Sodium N-Lauroyl Sarcosinate commercially available from Croda
under the commercial name of Crodasinic~ LS 30.
BHT is butylated hydroxy toluene.
Chelant* is a phosphonate chelant available under the trade name DEQUEST~
PA is an ethoxylated tetraethylenepentamine, average molecular weight 12,000.
The compositions I-VI described above were tested using the cleaning
performance and the anti-resoiling performance tests as described in the
section
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WO 00/26330 PCT/US99/22841
titled : Poly (vinyl methyl ether / malefic acid) copolymer. Composition I is
taken
as a reference, the other compositions are rated in panel score units against
the ,
reference composition I. Composition II is a composition comprising an
ethoxylated polyethylene amine (ESP-0620A~), which is an anti-resoifing agent
.
other than the poly (vinyl methyl ether I malefic acid) copolymers as
described in
the present invention. Compositions III to VI are compositions according to
the
present invention. Compositions I and II are comparative examples.
The above results clearly show the cleaning and anti-resoiling benefits of a
composition according to the present invention (compositions III to VI), i.e.,
compositions comprising a poly (vinyl methyl ether / malefic acid) copolymer,
versus compositions comprising no anti-resoiling polymer (composition I) or
compositions comprising other anti-resoiling polymers as claimed herein
(composition II).
Examples
The following examples will further illustrate the present invention. The
compositions are made by combining the listed ingredients in the listed
proportions (weight % unless otherwise specified).
Compositions VII Vill IX X XI XII
(weight %)
Hydrogen peroxide 4.0 4.0 5.0 6.0 -- ---
Gantrez S97~ 0.1 0.3 0.5 0.8 0.2 0.4
Water and minors Balance Balance Balance Balance Balance Balance
up to pH 6 fi.5 5 4 6 5
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41
Compositions XIII XIV XV XVI XVII XVIII
(weight %)
Hydrogen peroxide4.0 4.0 --- 6.0 4.0 4.0
Gantrez S97~ 0.2 0.3 0.1 -- 0.5 0.4
ESP-0620A~ 0.1 0.1 0.3 0.3 -_ 0.1
Lutensit K-187!50~0.1 -- --- 0.2 0.3 --
PVNO 0.5 0.4 0.2 0.5 1.0 2.0
PVPVI __ __- ___ 0.5 -_ __
PV/AA - --_ 0.3 --- __ __
PVP __ ___ ___ ~ 0.1 --
Ethanol 3.0 3.0 3.0 3.0 3.0 3.0
PA --- 0.1 0.2 0.1 -- 0.1
Sarcosinate 3.0 3.0 3.0 --- 2.5 3.0
BHT ~ 0.01 0.01 0.02 0.01 -- 0.01
AMCP - --- -_ --- 0.5 -
Chelant' 0.2 0.2 0.2 0.2 0.3 0.3
Na CnAS - --- - 3.0 0.5 --
Salicylic Acid 0.5 0.5 0.5 0.5 -- 0.5
Propyl Gallate --- -- -- -- 1.0 --
NaOH 0.16 0.16 0.16 0.16 0.06 0.26
Water and minorsBalance Balance Balance Balance Balance Balance
up to pH 6 6 6 6 3.5 8
Gantrez S97~ is poly (vinyl methyl ether I malefic acid) copolymer
commercially
available from (SP Corporation.
ESP-0620A~ is ethoxylated polyethylene amine commercially available from
Nippon Shokubai CO., LTD.
~utensit K-1871500 is an ethoxylated polyethylene amine commercially available
from BASF.
PVP is Poly Vinyl Pyrrolidone commercially available from BASF.
PVNO is Poly(4-Vinylpyridine-N-Oxide) (Mw 20,000) commercially available from
Reilly.
PVIAA is N-vinylpyrrolidone and Acrylic Acid copolymer commercially available
under the trade name Sokalan~ PG 310.
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42
PVPVI is N-vinyipyrrolidone and N-vinylimidazole co-polymer commercially
available under the trade name Sokaian~ PG55.
Sarcosinate is Sodium N-Lauroyl Sarcosinate commercially available from Croda
under the commercial name of Crodasinic~ LS 30.
BHT is butylated hydroxy toluene.
AMCP is acrylic/maleic based copolymers commercially available under the trade
name Sokalan CP5~.
Chelant* is a phosphonate chelant available under the trade name DEQUEST~
Na CnAS is sodium alkyl sulphate.
PA is an ethoxylated tetraethylenepentamine, average molecular weight 12,000.
The compositions exemplified above are preferably packaged in a container
adapted to deliver a spray of droplets having a particle size distribution
with a
mean diameter D(v,0.9) of 200 to 400 microns, when measured with Malvern
Mastersizer S LongBed ~ referenced herein before. A suitable container used
was an electrically driven sprayer.
The compositions in the examples above deliver excellent anti-resoiling
properties as well as excellent cleaning performance on particulate soil,
greasy/oily soil, and/or enzymatic soil as well as on other types of soils.
