Note: Descriptions are shown in the official language in which they were submitted.
08295/249W01
CA 02278026 1999-07-15
CARPET CLEANING COMPOSITIONS HAVING INCREASED
LEVELS OF AMINOPOLYCARBOXYLIC ACIDS AS
ANTI-RESOILING AGENTS
The present invention relates to carpet cleaning and treatment compositions.
Carpets provide a pleasant surface covering, especially flooring surfaces, and
in
some cases wall surfaces, carpets are durable, helps deaden sound
transmission, are
somewhat thermally insulating, and are readily applied. In order to retain
their attractive
appearance, such carpet surfaces require maintenance, particularly cleaning.
Frequently,
at the time of their production, carpets or carpet fibers are treated with a
variety of known
compounds to provide the carpet fibers with a degree of repellency,
particularly to oil and
water. Both oil and water, jointly and severally, are major constituents in a
wide variety
of staining materials, such as: beverages, food stuffs, as well as other
edible and/or
imbibable compositions. Further staining compositions include any variety
number of
other materials which may come into contact with the carpet and which are
entrained
amongst the carpet fibers and/or upon the carpet fiber surface. Unfortunately,
such
carpet fiber treatments frequently wear away with time due to the normal wear
and tear
associated with such an installed carpet surface, and/or may be deleteriously
degraded
and/or removed by one or more chemicals or other compositions which may be
used in
the intensive cleaning of a carpet surface.
Exemplary prior art compositions include those described in US 5338475; US
5370919; EP 0648834 and WO 95/14578.
While prior art compositions have met with varying degrees of success, it
should
be apparent that there exists a real and present need in the art for improved
carpet
cleaning compositions which are effective in removing stains from soiled
carpet surfaces
and from soiled carpet fibers. Such a composition desirably provides an
efficacious
cleaning benefit, and also imparts a recoiling resistance to carpet surfaces
cleaned with
the composition.
The present invention provides improved liquid carpet cleaning compositions,
and improved processes for cleaning and treating carpets.
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AP~1F~ :~D~r ~H~~T
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' WO 98J31776 PCT/US97/19217
Summar;~of the Invention and Detailed Descri ton:
In accordance with one aspect of the present invention there is provided an
aqueous flowable carpet cleaning composition which comprises the following
constituents:
A) one or more surfactant compounds selected from anionic, nonionic and
amphoteric surfactant compounds;
B) an aminopolycarboxylic acid salt as an recoiling inhibiting agent;
C) an organic solvent; and,
D) optionally, a stain repellency imparting composition especially a fluorine
containing compound.
These aqueous carpet cleaning compositions may include one or more further
optional constituents including but not limited to: further organic solvents
or co-
solvents, further recoiling inhibiting agents, chelating agents, fragrances,
preservatives, viscosity modifying agents such as thickening agents,
preservatives, pH
1 S adjusting agents, pH buffers, agents for imparting water repellency to
carpets and
carpet fibers, and agents for imparting oil repellency to carpets and carpet
fibers
whose total weight generally comprise not more than about 20%wt., preferably
not
more than 10% by weight of the compositions described.
The present inventor has made the surprising discovery that in the place of,
or
in addition to, known anti-recoiling agents which are known to be useful in
carpet
cleaning and treatment compositions, increased amounts of an
aminopolycarboxylic
acid salts, especially salts of ethylenediaminetetraacetic acid are useful as
recoiling
inhibiting agents (also sometimes referred to as anti-recoiling agents). Such
an effect
has surprisingly been observed in compositions which include as well as those
which
do not include one or more further conventionally known resoiiing inhibiting
agents.
This is a significant discovery as it permits the use of low cost and widely
available
aminopolycarboxylic acid salts to be used in the place of or in conjunction
with one or
more further conventionally known recoiling inhibiting agents.
The aqueous carpet cleaning and treatment compositions according to the
invention include (A) one or more surfactant compounds selected from anionic,
nonionic and zwitterionic surfactant compounds.
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~. t.
.,
,.. . . ,
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WO 98/31'796 PCT1US97/19217 - --
Exemplary useful anionic surfactants include known art compounds, including
organic sulfuric reaction products having in their molecular structure an
alkyl group
containing from about 8 to about 20 carbon atoms and a sulfonic acid or
sulfuric acid
ester group. Included in the term "alkyl" is the alkyl portion of aryl groups.
These
include but are not limited to: alkali metal salts, ammonium salts, amine
salts,
aminoalcohol salts or the magnesium salts of one or more of the following
compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates,
alkylaryl
polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide
sulfonates,
alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl
sulfosuccinates, alkyl
ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate,
alkyl
sulfoacetates, alkylpolyglycosides, diphenyl sulfonate derivatives, alkyl
phosphates,
alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl
taurates.
Generally, the alkyl or acyl radical in these various compounds comprises a
carbon
chain containing 8 to 20 carbon atoms, and preferably comprises a carbon chain
1 S containing 12 to 20 carbon atoms, The alkyl or acyl radical may be linear
or branched.
Mixtures of two or more anionic surfactants may be used as well. Further
exemplary
anionic surfactants which may be used include fatty acid salts, including
salts of oleic,
ricinoleic, palmitic, and stearic acids; copra oils or hydrogenated copra oil
acid, and
acyl lactylates whose acyl radical contains 8 to 20 carbon atoms. Other
anionic
surfactants not particularly enumerated here may also find use in conjunction
with the'
compounds of the present invention.
Preferred as the anionic surfactant constituent are alkyl sulfates, alkyl
benzene
sulfates, and alkane sulfonates, particularly water soluble salts thereof and
especially
preferred are those containing from 11 to 17 carbon atoms in their alkyl
radical, which
may be straight chained or branched. Useful water soluble salts which are
effective
in producing salt forms of the surfactant include, but are not limited to:
sodium,
potassium, ammonium, magnesium, chloride and mono-, di- and tri- C,-C, alcohol
ammoniums, amine and aminoalcohol salts forms. Desirably, the anionic
surfactants
are ones which may be characterized as having a low chloride content.
Exemplary preferred alkyl sulfates include sodium lauryl sulfate, alkyl
benzene sulfates, and alkane sulfonates particularly ones characterized as
having a low
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chloride content. Desirably the anionic surfactant is also selected to be of a
type
which dries to a friable powder. Such a characteristic facilitates the
subsequent
removal of such anionic surfactants from a fibrous substrate, especially
carpets and.
carpet fibers, such as by bnishing or vacuuming.
The anionic surfactant according to constituent (A) may be included in the
present inventive compositions in an amount of from 0 - 5 %wt., but is
desirably
included in amounts of from 0.1 - 2% wt., and most desirably is included in
amounts
of 0.5 - 1.5% wt. which provides advantageous cleaning properties to the
inventive
compositions. Such recited weights are based on the weight of anionic
compounds or
"actives" in an anionic surfactant containing preparation. Also, as noted
previously, a
plurality of anionic surfactants may be used.
The compositions according to the invention also include minor amounts of
one or more nonionic surfactants particularly alkoxylated aliphatic primary
alcohols
and alkoxylated aliphatic secondary alcohols. Such include for example C$
C,°
primary or secondary aliphatic alcohols condensed with from 2 - 10 moles of
one or
more alkylene oxides. Such alkoxylated compounds specifically include ethylene
oxide, propylene oxide and butylene oxides, of which ethylene oxide, propylene
oxide, or mixtures thereof are preferred, and further of which condensates
containing
only ethylene oxide as the alkoxyl moiety is most preferred.
Desirably the nonionic surfactant constituent, when present, is selected from
alkoxylated Cx - C,; primary aliphatic alcohols, and an alkoxylated C,o C,5
secondary
aliphatic alcohol in which ethylene oxide and/or propylene oxide represents
the
alkoxylate moiety of such surfactants.
Illustrative examples of these preferred water soluble nonionic ethoxylated
phenols and/or ethoxylated alcohols surfactants C,, - C" linear primary
alcohols which
include an average of 6 ethoxy groups per molecule, C" - C,; secondary alcohol
which includes an average of 9 ethoxy groups per molecule, alkoxylated linear
aliphatic C~- C") alcohol having a number of both ethoxy and propoxy groups
per
molecule, and C,° - C,, alkoxylated fatty alcohols.
Other known nonionic surfactant compounds are contemplated as being useful
in the compositions according to the present invention and these include
alkoxylated
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alkyl aromatic compounds. Such compounds contain at least one aromatic moiety,
such as a phenol, as well as an alkyl chain, which may be straight chained or
branched. Desirably the aromatic moiety is CS C" and particularly C6 aromatic
moieties are preferred, and wherein the alkyl chain is a CR-C2° alkyl
group. The
alkoxyl groups in such may be ethylene oxide, propylene oxide and butylene
oxides,
of which ethylene oxide, propylene oxide, or mixtures thereof are preferred,
and
further of which ethylene oxide is most preferred.
Such alkoxylated alkyl aromatic compounds include nonyl phenol ethoxylates,
isooctyl phenol ethoxylates and particularly a C,~ C,, ethoxylated octyl
phenol with an
average of 1.5 ethoxy groups per molecule.
Nonionic surfactants according to constituent (A) may be included in the
present inventive compositions in an amount of from 0 - 5% wt., desirably from
0.001
-1 % wt., more desirably are included in amounts of from 0.05 - 0.5%wt., and
most
desirably are included in amounts of from 0.1 - 0.3 %wt. which amounts provide
advantageous cleaning properties to the inventive compositions. Such recited
weights
are based on the weight of nonionic compounds or "actives" in a nonionic
surfactant
containing preparation. It is also to be understood that a plurality of
nonionic
surfactants may be used.
The amphoteric surfactant according to constituent (A) may be any of a
number of compounds known to the art, including amphoteric imidazolinium
derivatives, and especially betaines such as alkylbetaines and
amidoalkylbetaines.
The amphoteric surfactants of constituent (A), when present, may be included
in the
present inventive compositions in an amount of from 0 - 5% wt., but is
desirably
included in amounts of from 0 - 2% wt., and most desirably is included in
amounts of
from 0 - 1 % wt. which provides advantageous cleaning properties to the
inventive
compositions. Such recited weights being based on the weight of amphoteric
compounds or "actives" in an amphoteric surfactant containing preparation.
Such
recited weights being based on the weight of amphoteric compounds or "actives"
in a
amphoteric surfactant containing preparation. Also, it is contemplated that a
plurality
of amphoteric surfactants may be used.
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' WO 98131776 PCT/US97119217 - --
It is to be understood that the total of the combined weights of the anionic,
nonionic and amphoteric surfactants denoted are present in the inventive
compositions
in an amount of from 0.1 - 1 I %wt., but are desirably present in amounts of
from 0.15
- 4.5%wt., and most desirably are present in amounts of from O.G - 2.8%wt.
The compositions of the invention include (B} an aminopolycarboxylic acid
salt as an resoiling inhibiting agent. The aminopolycarboxylic acids are
compounds
in which the amino nitrogen is attached to two or more substituent groups.
Many
such aminopolycarboxylic acids and their salts are known to the art. Preferred
for use
as the aminopolycarboxylic acid salt constituent in the present inventive
compositions
are the salts of ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid,
and N-hydroxyethytethylenediaminetriacetic acid, as well as mixtures thereof.
The
preferred salts of these acids are the potassium and the sodium salts, of
which two the
sodium salt is generally to be preferred. The aminopolycarboxylic acid salt
(B) is
desirably present in amounts of from 0.1 - 50 %wt., more desirably from about
0.5
6.0 %wt., and most desirably from 1.0 to 3.0 %wt.
It has been surprisingly been discovered by the inventor that carpet cleaning
compositions may be provided with a significant amount of soil redeposition
inhibition by the incorporation into their formulations of amounts of salts of
aminopolycarboxylic acid, especially ethylenediaminetetraacetic acid. What is
further surprising is that such an inclusion may be in conjunction to the use
of one or
more fluorochemicals which are known to the art to inhibit soil redeposition,
or that
the such fluorochemicals may be wholly absent from such formulations and due
to the
inclusion the treated carpet still exhibits an excellent soil redeposition
inhibition
effect.
The aqueous carpet cleaning compositions include as constituent (C) an
organic solvent constituent which may be a single solvent or which may be a
mixture
of two or more organic solvents. A wide range of known materials may be used
and
without limitation these include water soluble or miscible alcohols, glycols,
acetates,
ether acetates and glycol ethers. Exemplary such aicohols useful in the
compositions
of the invention include C,-CK alcohols which may be straight chained or
branched,
and which are specifically intended to include both primary, secondary and
tertiary
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WO 98131776 PCT/US97/19217
alcohols. Exemplary glycol ethers include those glycol ethers having the
general
structure R~ O-Re-OH, wherein Ra is an alkoxy of 1 to 20 carbon atoms, or
aryloxy of
at least 6 carbon atoms, and R,, is an ether condensate of propylene glycol
and/or
ethylene glycol having from one to ten glycol monomer units. Preferred are
glycol
ethers having one to five glycol monomer units. These are C,-C,° glycol
ethers.
By way of further non-limiting example specific organic solvents include
propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene
glycol
methyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether,
diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene
glycol,
ethylene glycol, isopropanol) ethanol, methanol, diethylene glycol monoethyl
ether
acetate and particularly advantageously ethylene glycol hexyl ether,
diethyiene glycol
hexyl ether, as well as the C,-Cg primary and secondary alcohols. Many such
organic
solvents are presently commercially available. The organic solvent (C)
constituent is
desirably present in amounts of to about 20 %wt., more desirably from about
0.1 - 5
%wt., and most desirably from 0.1 to 3.0 %wt.
Desirably the one or more organic solvents which make up the organic solvent
constituent (C) exhibit a low vapor pressure, particularly less than 0.05 mm
Hg at a
temperature of 25°C. Such preferred organic solvents ensure quick
evaporation from
treated carpets or other fibrous surfaces, and also minimize the residence
time of any
films formed by the inventive compositions on such treated surfaces, which in
turn
improves the anti-recoiling characteristics of the inventive compositions.
As is noted above, the compositions according to the invention are aqueous in
nature. Water is added to order to provide to 100% by weight of the
compositions of
the invention, and is preferably substantially free of any undesirable
impurities such
as organics or inorganics, especially mineral salts.
As has been previously noted, the compositions of the invention may include
one or more optional constituents many of which are recognized as conventional
additives to aqueous carpet cleaning or treatment compositions.
One optional constituent which is desirably included is one or more chelating
agents. Useful as chelating agents include those known to the art, inter alias
gluconic
acid, tartartic acid, citric acid, oxalic acid) lactic acid, nitrilotriacetic
acid, polyacrylic
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WO 98/31776 PGT/U897119217 - -
acid salts, diethylene triamine pentaacetic acid, and their water soluble
salts,
especially the alkali metal salts and particularly the sodium salts thereof,
as well as
aminopolycarboxylic acids and salts thereof wherein the amino nitrogen has
attached
thereto two or more substituent groups, including the sodium and potassium
salts of
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-
hydroxyethylethylenediaminetriacetic acid which have been described above with
reference to constituent (B). In the case that a chelating agent is added
other than a
aminopolycarboxylic acids and salts, it is generally added in only minor
amounts, i.e.,
less than about 0.5%wt. but due to the amount of the aminopolycarboxylic acids
and
salts present as constituent (B), the use of a further chelating agent is
generally not
necessary.
As a further optional constituent there may be advantageously included is a
preservative constituent. As a significant portion of the formulation
comprises water,
it is preferably that the preservative be water soluble. Such water soluble
preservatives include compositions which include parabens, including methyl
parabens and ethyl parabens, glutaraldehyde, formaldehyde, 2-bromo-2-
nitropropane-
I,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3-
one, and
mixtures thereof.
The compositions according to the invention optionally but desirably include
an amount of a pH adjusting agent or pH buffer composition. Such compositions
include many which are known to the art and which are conventionally used. By
way
of non-limiting example pH adjusting agents include phosphor containing
compounds, monovalent and polyvalent salts such as of silicates, carbonates,
and
borates, certain acids and bases, tartarates and certain acetates. By way of
further
non-limiting example pH buffering compositions include the alkali metal
phosphates,
polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates,
metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the
same. Certain
salts, such as the alkaline earth phosphates, carbonates, hydroxides, can also
function
as buffers. It may also be suitable to use as buffers such materials as
aluminosilicates
(zeolites), borates, aluminates and certain organic materials such as
gluconates,
succinates, maleates, and their alkali metal salts. Desirably the compositions
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CA 02278026 1999-07-15
' wo ~3m~s rc~rrtrs9~nni~ ~ --
according to the invention include an effective amount of an organic acid
and/or an
inorganic salt form thereof, which may be used to adjust and maintain the pH
of the
compositions of the invention is the desired pH range. Particularly useful is
citric acid
and sodium citrate which are both widely available and which are effective in
providing these pH adjustments and buffering effects.
Further useful optional constituents include optical brighteners, including
those based on stilbene derivatives and distyrylbiphenyl derivatives.
Oxidizing agents
known to the art, including hydrogen peroxide, may be used in the inventive
compositions however as these are frequently unstable and their efficacy is
known to
quickly degrade over time making their use to be desirably avoided.
The compositions of the invention may optionally include one or more
constituents which are intended to modify the visual appearance thereof, such
as one
or more coloring agents, such as dyes and/or pigments, as well as compositions
which
act as opacifiers. These are generally included in only minor amounts, but are
desirably omitted.
The compositions of the invention may also optionally include fragrance
compositions or other composition for modifying the scent characteristics of
the
inventive compositions. Such may be any of a number of known materials,
including
those known to be effective in absorbing odors, those luiown useful in masking
odors,
as well as those which are known to impart or provide a specific scent.
Fragrances,
whether naturally or synthetically produced may be used in the inventive
compositions.
Although the inventive compositions provide excellent anti-resoiling
characteristics when they include only an aminopolycarboxylic acid salt as a
recoiling
inhibiting agent, the use of one or more further anti-resoiling agents is
contemplated.
Such compositions include compounds exhibiting an anti-recoiling effect for
example,
colloidal silica, aluminum oxides, styrene-malefic anhydride copolymer resins,
polyvinylpyrrolidone, polyacrylates, polycarboxylates, modified cellulose
polymers,
vinyl acetate/maleic anhydride copolymer resins, cationic amines, aliphatic
quaternary
ammonium salts known to have anti-static properties, imidazoline salts as well
as
others known to the art. Such compounds which inhibit resoiling may be added
in
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WO 98/31776 PCT/US97/19217
amounts of from 0 - 2%wt., but when present are desirably included in amounts
of
from 0.001 %wt - 1 %wt.
Particularly preferred anti-recoiling compounds useful in the present
inventive
compositions are fluorinated acrylic polymers; the inclusion of such
fluorinated
acrylic polymers and salts in the compositions of the invention improves the
recoiling
resistance of fibrous substrates treated with said compositions. A specific
and
preferred fluorinated acrylate copolymer is one which confonms to the formula
(C):
CF3(CF2)~CH20COC(CH3)=CHZ (C)
wherein
n represents a value of from 6 - 8.
This fluorinated acrylate copolymer may be generally characterized by a total
fluorine content based on polymer solids of approximately O.G percent. This
fluorinated acrylate copolymer may also contain a zinc complex to act as a
crosslinker. The number average (Mn) and weight average (Mw) molecular weights
are generally in the range of approximately 9,000 and approximately 10,500
respectively. Such a fluorinated acrylate copolymer may be obtained
commercially as
a water based dispersion of approximately 76-77 weight % water; 18-19 weight
acrylate copolymer; 1 weight % nonylphenoxypolyethoxyethanol; 1 weight %
sodium
lauryl sulfate; and 1 weight % zinc oxide complex (with said weight % of the
ingredients based on the total weight of the water dispersion), as SYNTRAN~
1575
(Interpolymer Corporation, Canton, MA). When this SYNTRAN~ 1575 composition
is employed as constituent (b), it may be included in the present inventive
compositions in amounts such that the fluorinated acrylate copolymer is
present from
0.001 - 2%wt., desirably in amounts of from 0.001 %wt - 0.75%wt., and most
desirably in amounts of from 0.05%wt. - 0.5%wt. with such recited weights
being
based on the weight of the fluorinated acrylic polymers and/or salts thereof
present.
One further particularly anti-resoiling compound particularly useful in the
present inventive compositions is a non-halogenated, especially a non-
fluorinated,
acrylic polymer compound which may be represented by the formula (D):
(-CH2 CH(COOR)-)" (D)
wherein
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08295/249W01
CA 02278026 1999-07-15
n is a value greater than 50.
Such a non-fluorinated acrylic polymer is presently commercially available and
may
be obtained as an aqueous dispersion which includes 78-79%wt. water, 18-19%wt.
of
the non-fluorinated acrylic polymer, 1 %wt. of sodium lauryl sulfate, 1 %wt.
sodium
nonylpehnoxypolyethoxyethanol sulfate, and 1 %wt. zinc oxide complex as
SYNTRAN~ 1580, as well as an aqueous dispersion which includes 74-75%wt.
water, 23-24%wt. of the non-fluorinated acrylic polymer, 1 %wt. of sodium mono-
alkylarylpolyethoxy sulfosuccinate, and 1 %wt. sodium lauryl sulfate sulfate
as
SYNTRAN~1588. These materials are considered to be infinitely miscible in
water
by the manufacturer, and the former is provided as an aqueous dispersion
having a pH
of 8.3 to 9.3, and the latter is provided as an aqueous dispersion having a pH
of 7.7 to
8.7. Both of these materials may be obtained from Interpolymer Corporation
(Canton,
MA).
As noted previously, the inventive compositions may include one or more
further
optional constituents which impart a degree of water repellency, oil
repellency or both
water and oil repellency to carpet fibers and carpet surfaces. These include
for example,
compositions recited in U.S. Patent No. 4,145,303 and U.S. Patent No.
3,901,727 both to
Loudas, U.S. Patent No. 5,370,919 to Fieuws as well as those described in
commonly
assigned, U.S. Patent No. 5,712,240 and U.S. Patent No. 5,861,365.
An advantageously used material for imparting water and/or oil repellency to
the compositions of the invention includes a fluoroaliphatic oligomer or
polymer (the
term oligomer hereinafter includes polymer unless otherwise indicated)
represented by
the general formulae ( 1 ) and (2):
(R~)SZI(R3),,~'B1t (1)
((Rr)sZI(R3)y.Z'B'l~w (2)
where
R, is a fluoroaliphatic radical,
Z is a linkage through which R, and (R3)y moieties are covalently bonded
together,
-- 11 --
..:.. . ,
_. v ; .v--
a . ~;= _. _ .
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(R3)y is a poly(oxyalkylene) moiety, R3 being an oxyalkylene group with 2 to 4
carbon atoms and y is an integer (where the above formulas are those of
individual compounds) or a number (where the above formulas are those of
mixtures) at least 1, preferably 1 to 125 and can be as high as 180 or higher,
B is a hydrogen atom or a monovalent terminal organic radical,
B' is B or a valence bond, with the proviso that at least one B' is a valence
bond
interconnecting a Z-bonded R3 radical to another Z,
Z' is a linkage through which B, or B', and R3 are covalently bonded together,
s is an integer or number of at least 1 and can be as high as 25 or higher,
t is an integer or number of at least i, and can be as high as 60 or higher,
and
w is an integer or number greater than 1, and can be as high as 30 or higher.
In formulas ( 1 ) and (2), where there were a plurality of R, radicals, these
may
be either the same or different. This also applies to a plurality of Z, Z',
R3, B, B', and,
in formula (2), a plurality of s, y and t.
R, is a stable, inert, nonpolar, preferably saturated monovalent moiety which
is
both oieophobic and hydrophobic. A fluorinated oligomer preferably comprises
from
1 to about 25 R, groups and preferably comprises about 5 percent to about 30
percent,
and more preferably about 8 percent to about 20 percent fluorine by weight
based on
the total weight of the oligomer, the loci of the fluorine being essentially
in the R,
groups. R, preferably contains at least about 3 carbon atoms, more preferably
3 to
about 20 carbon atoms, and most preferably about G to about 12 carbon atoms.
R, can
contain straight chain, branched chain, or cyclic alkyl groups. R~ is
preferably free of
polymerizable olefinic unsaturation and can optionally contain caternary
heteroatoms
such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred
that each R~
contain about 40%.to about 78% fluorine by weight, more preferably about 50%
to
about 78% fluorine by weight. The terminal portion of the R, group contains a
fully
fluorinated terminal group. This terminal group preferably contains at least 7
fluorine
atoms, e.g., CF3CF2CF2; (CF3)zCF; CFZSFS, or the like.
Perfluorinated aliphatic groups, i.e., those of the formula C"F2"+~, are the
most
preferred embodiments of R~
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' WO 98/31T16 PCT/US97/19217 _
Generally, the oligomers will contain about S to 40 weight percent, preferably
about 10 to 30 weight percent, of carbon-bonded fluorine.
In the poly(oxyalkylene) radical, (R3)y, R3 is an oxyalkylene group having 2
to 4 carbon atoms, such as -OCHZCHZ , -OCHZCHZCHZ , -
OCHZCH2CH2CH2 ,
-OCH(CH3)CHz , and -OCH(CH3)CH(CH3)-, the oxyalkylene units in said
poly(oxyalkylene) being the same, as in poly(oxypropylene), or present as a
mixture,
as in a heteric straight or branched chain or randomly distributed
oxyethylene,
oxypropylene and oxybutylene units or as in a straight or branched chain of
blocks of
oxyethylene units and/or blocks of oxypropylene units and/or blocks of
oxybutylene
units. The poly(oxyalkylene) chain can be interrupted by or include one or
more
catenary linkages. Where said catenary linkages have three or more valences,
they
provide a means for obtaining a branched chain of blocks of oxyalkylene units.
The
poly(oxyalkylene) radicals in the oligomers can be the same or different, and
they can
be pendent. The molecular weight of the poly(oxyalkylene) radical can be about
500
to 2,500 and higher, e.g., 100,000 to 200,000 or higher.
The function of the linkages Z and Z' is to covalently bond the
fluoroaliphatic
radicals, R,, the poly(oxyalkylene moieties, (R3)y and radicals B and B'
together in the
oligomer. Z and Z' can be a valence bond, for example, where a carbon atom of
a
fluoroaliphatic radical is bonded or linked directly to a carbon atom of the
poly(oxyalkylene) moiety. Z and Z' each can also comprise one or more linking
groups such as polyvalent aliphatic and polyvalent aromatic, oxy, thio,
carbonyl,
sulfone, sulfoxy, phosphoxy, amine, and combinations thereof, such as
oxyalkylene,
iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamidoalkylene,
carbonamidoalkylene, urethane, urea, and ester. The linkages Z and Z' for a
specific
oligomer will be dictated by the ease of preparation of such an oligomer and
the
availability of necessary precursors thereof.
Illustrative linking groups Z are alkylene groups, such as ethylene,
isobutylene, hexylene, and methylenedicyclohexylene, having 2 to about 20
carbon
atoms, aralkylene groups, such as
-- 13 --
CA 02278026 1999-07-15
' WO 98/31776 PG"T/US97119217
-CHy~CHZ ~CH2~
and ~ ~/ having up to 20 carbon
atoms, aryiene groups, such as tolylene, -CBH3(CH3) -, poly(oxyalkylene)
groups,
such as
-(CZH40)yCZH4 where y is 1 to about 5, and various combinations of these
groups.
Such groups can also include other hetero moieties (besides -O-), including -S
and -N-. However, Z is preferably free of groups with active hydrogen atoms.
From the above description of Z and Z' it is apparent that these linkages can
have a wide variety of structures, and in fact where either is a valence bond,
it does
not even exist as a structure. However large Z or Z' is, the fluorine content
(the locus
of which is R,) is in the aforementioned limits set forth in the above
description, and
in general the total Z and Z' content of the oligomer is preferably less than
10 weight
percent of the oligomer.
The monovalent terminal organic radical, B, is one which is covalently bonded
through Z', to the poly(oxyalkylene) radical.
Though the nature of B can vary, it preferably is such that it complements the
poly(oxyalkylene) moiety in maintaining or establishing the desired solubility
of the
oxyalkylene. The radical B can be a hydrogen atom, an acyl radical such as
CsHSC(O~, an alkyl radical, preferably lower alkyl, such as methyl,
hydroxyethyl,
hydroxypropyl, mercaptoethyl and aminoethyl, or an aryl radical, such as
phenyl,
chlorophenyl, methoxyphenyl, nonylphenyl, hydroxphenyl, and aminophenyl.
Generally, Z'B will be less than 50 weight percent of the (R3)~'B moiety.
The fluoroaliphatic radical-containing poly(oxyalkylene) compounds used in
the compositions according to the present invention can be prepared by a
variety of
known methods, such as by condensation, free radical, or ionic
homopolymerization
or copolymerization using solution, suspension, or bulk polymerization
techniques,
e.g., see "Preparative Methods of Polymer Chemistry", Sorenson and Campbell,
2nd
ed., Interscience Publishers.
Many of such fluoroaliphatic radical-containing poly(oxyalkylene) compounds
are presently commercially available.
-- 14 --
CA 02278026 1999-07-15
WO 9$131776 PCTIUS97/19217
In one preferred embodiment of the invention the fluoroaliphatic radical-
containing poly(oxyalkylene) compound contains a fluoroalkyl radical having 3
to 20
carbon atoms, wherein perfluoroalkyl radicals are particularly preferred.
In a further preferred embodiment the fluoroaiiphatic radical-containing
poly(oxyalkylene) compound can contain 1 to 15, but more preferably 1-2, and
most
preferably an average of about 1.5 ethylene and/or propylene radicals per
molecule of
the fluoroaliphatic radical-containing poly(oxyalkylene) compound.
Particularly preferred is the fluoroaliphatic radical-containing
poiy(oxyalkylene) compound include those which may be represented by the
following general structural formula (3):
CaF28+,N(CHs)(W)a(A)~B X' (
in which:
B represents a water soluble group selected from sulfate, sulfonate,
carboxylate,
phosphate, phosphonate or halogen group;
W represents a lower alkyl group especially a -CH2-, -CHZCHZ- and/or
-CH2CH2CH2 ;
A represents an ethoxy (OCZH4), propoxy (OC3Hs), and/or butoxy (OC4H8) or a
mixture of two or mere such groups;
X+ is a salt forming counterion such as an organic counterion, or an inorganic
counterion such as an alkali or alkaline earth metal counterion.
n represents a value of between I and 8, preferably is a value of from 1 to 5
inclusive, and most preferably is a value of from about 1 to about 3;
a represents a value of between 1 and 12) preferably is a value of from 5 to
12
inclusive, and most preferably is a value of from about 6 to about 9;
A particularly advantageous fluoroaliphatic radical-containing
poly(oxyalkylene) compound which may be used as constituent (a) of the present
invention is one which is presently commercially available as Fluorad~ FC-138
from
the Minnesota Mining and Manufacturing Co. (St. Paul, MN) which is described
as
being a composition consisting essentially of: 37% wt. water, 27% wt. of the
-- 15 --
CA 02278026 1999-07-15
' wo 9smr~6 rc~r~s97n9zm - --
fluorochemica! salt, 18%wt. of isopropyl alcohol, and 18%wt. of 2-
butoxyethanol.
While not wishing to be bound to the following representation, it is believed
that this
advantageous fluoroaliphatic radical-containing poly(oxyalkylene) compound is
a
fluorochemical salt is extremely similar to or
which may be represented by the following general structural formula (4):
C8F"N(CH3)(CHZ)3(A)~OS02 X+ (4)
in which:
n represents a value of between 1 and 3, preferably is a value of from 1 to 2
inclusive, and most preferably is a value of about 1.5;
A represents an ethoxy (OCZH4) group, propoxy (OC3H6) group, or a mixture of
such groups, but preferably represents ethoxy;
X+ is a salt forming counterion such as an alkali or alkaline earth metal
counterion.
The fluoroaliphatic radical-containing poly(oxyalkylene) compound according
to constituent (a) is included in the compositions of the invention in amounts
of from
between about 0.001 %wt. to about 3%wt.; more desirably the fluoroaliphatic
radical-
containing poly(oxyalkylene) compound is present in an amount of from 0.1 %wt.
and
0.5%wt. based on the total weight of the composition. It is understood that
such
fluoroaliphatic radical-containing poly(oxyalkylene) compound may be provided
with
further constituents, such as water, one or more surfactants in commercial
preparations.
These are described in further detail in U.S. Patent No. 5,370,919 to Fieuws,
as noted
above.
Particularly advantageously used materials which may impart water and/or oil
repellency to treated substrates include certain fluorosurfactant compositions
which
may be added in amounts which facilitate the oil repellent, viz., the
oleophobic
characteristics of substrates treated with the compositions being taught
herein. One
such exemplary further fluorosurfactant composition which is desirably
included in the
compositions of the invention is a perfluoropropionate according to the
formula:
-- i G --
CA 02278026 1999-07-15
WO 98131776 PCT/US97/19217 - --
F(CFZ)~ CHZCH2-S-CHZCH2-COO'X' (A)
where:
n is an integer having a value of 6 to 12; and,
X' is a salt forming counterion, preferably lithium.
Another such exemplary further fluorosurfactant composition includes a
perfluoroalkyl phosphate or salt thereof according to the formula (B):
O
CF3-CF2(CF2CF2)n-CH2CH2-O- ~ =O (B
O
where:
n is an integer having a value of from 6 to 12.
These fluorosurfactant compositions according to formulae (A) and (B) may be
used
singly, or may be used in a mixture. When used as a mixture, desirably the
weight ratio
of the perfluoropropionate to the perfluoroalkyl phosphate is in the range of
firom about
1:1 to 1:2. Such a mixture is presently commercially available as ZONYL~ 7950.
Such fluorsurfactant compositions include those which are described in US
5,439,610 to
Ryan, et al., the contents of which patent are herein incorporated by
reference.
Additional exemplary further fluorosurfactant compositions which are desirably
included in the compositions of the invention include materials are presently
commercially available under the tradena~ne ZONYLO from E.I. DuPont de Nemours
Co. Exemplary materials include ZONYL~ FSA which is described as being
F(CF2CF2)~8CH2CH2SCH2CHZCOZLi; ZONYLm FSP which is described as being
(F(CFZCF2)3$CH2CH20)P(O)(ONH,)2; ZONYL~ FSE which is described as being
(F(CF2CFz)3~CHZCH20)ZP(O)(ONH,)2; ZONYL~ UR which is described as being
(F(CFZCF2)s.8CH2CH20)P(O)(OH)Z as well as (F(CFZCF2)~CHZCH20)ZP(O)(OH);
ZONYL~ FSJ which is described as being (F(CF2CF2)3$CH2CH~0)P(O)(ONH4)2 in
conjunction with a nonfluorinated surfactant; ZONYL~ TBS which is described as
being F(CFZCF2)~CHZCH2S03H as well as F(CFzCF2)3$CH2CHZS03NH4. Each of
these materials may be used jointly such as in a mixture of two or more
__ 17 __
CA 02278026 1999-07-15
WO 98/31776 PCT/IJS97/19217
flurorosurfactants, or singly. Of these materials, those available as ZONYL~
7950 are
particularly preferred.
A yet further material which improves the resoiling resistance of fibrous
substrates treated of the inventive compositions are certain fluorinated
acrylic
polymers,_including those which conform to the formula (C):
CF3(CF2)~CH20COC(CH3)=CH2 (C)
wherein
n represents a value of from 6 - 8.
This fluorinated acrylate copolymer may be generally characterized by a total
fluorine content based on polymer solids of approximately 0.6 percent. This
fluorinated acrylate copolymer may also contain a zinc complex to act as a
crosslinker. The number average (Mn) and weight average (Mw) molecular weights
are generally in the range of approximately 9,000 and approximately 10,500
respectively. Such a fluorinated acrylate copolymer may be obtained
commercially as
I S a water based dispersion of approximately 76-77 weight % water; 18-19
weight
acrylate copolymer; I weight % nonylphenoxypolyethoxyethanol; I weight %
sodium
lauryl sulfate; and 1 weight % zinc oxide complex (with said weight % of the
ingredients based on the total weight of the water dispersion), as SYNTRAN~
1575
(Interpolymer Corporation, Canton, MA). When this SYNTRAN~ 1575 composition
is employed as constituent (b), it may be included in the present inventive
compositions in amounts such that the fluorinated acrylate copolymer is
present from
0.001 - 2%wt., desirably in amounts of from 0.001 %wt - 0.75%wt., and most
desirably in amounts of from 0.05%wt. - 0.5%wt. with such recited weights
being
based on the weight of the fluorinated acrylic polymers and/or salts thereof
present.
One further particularly useful anti-resoiling compound present inventive
compositions is a non-halogenated, especially a non-fluorinated, acrylic
polymer
compound which may be represented by the formula (D):
(-CHZ CH(COOR)-)~ (D)
wherein
n is a value greater than 50.
__ I g __
CA 02278026 1999-07-15
WO 98131776 PCT/US97/19217 - --
Such a non-fluorinated acrylic polymer is presently commercially available and
may
be obtained as an aqueous dispersion which includes 78-79%wt. water, 18-19%wt.
of
the non-fluorinated acrylic polymer, 1 %wt. of sodium lauryl sulfate, 1 %wt.
sodium
nonylpehnoxypolyethoxyethanol sulfate, and 1 %wt. zinc oxide complex as
SYNTRAN~ 1580, as well as an aqueous dispersion which includes 74-75%wt.
water, 23-24%wt. of the non-fluorinated acrylic polymer, 1 %wt. of sodium mono-
alkylarylpolyethoxy sulfosuccinate, and 1 %wt. sodium lauryl sulfate sulfate
as
SYNTRAN~1588. These materials are considered to be infinitely miscible in
water
by the manufacturer, and the former is provided as an aqueous dispersion
having a pH
of 8.3 to 9.3, and the latter is provided as an aqueous dispersion having a pH
of 7.7 to
8.7. Both of these materials may be obtained from Interpolymer Corporation
(Canton,
MA).
In the compositions according to the invention the total weight of such
optional constituents should not exceed about 20% by weight of the total
weight of
the composition, more preferably should not exceed about 10% by weight and is
most
preferably comprise less than about 7% by weight based on the total weight of
the
composition according to the invention.
It is to be understood that although the aqueous compositions taught herein
have been generally discussed in conjunction with the cleaning of carpets and
carpet
fibers, they may be used to treat fibers, textiles and fabrics. These include
those made
with or of one or more naturally occurnng fibers, such as cotton and wool,
regenerated
natural fibers including regenerated cellulose, and those made with or of
synthetically
produced fibers, such as polyamides, polyolefins, polyvinylidene chlorides,
acetate,
nylons, polyacrylics, rayon, and polyester fibers. Blends of two or more such
fibrous
materials are also expressly contemplated. Such textiles and fabrics may be
woven,
non-woven or knitted materials.
The compositions of the invention can be prepared in a conventional manner
such as by simply mixing the constituents in order to form the ultimate
aqueous
cleaning composition. The order of addition is not critical. Advantageously
ail of the
constituents other than water are added to a portion of the total amount of
water, and
then well mixed. Desirably the surfactants are first added to a volume of
water,
-- 19 __
CA 02278026 1999-07-15
WO 98/31776 PCTlUS97/19217 - "
followed by any remaining ingredients especially the optional constituents and
then
any remaining amount of water. In some cases, where certain of the desired
constituents (such as certain nonionic surfactants) are not liquids at room
temperature,
such may need to be melted, and/or dispersed in an aliquot of the volume of
water,
usually aided by a dispersing or solubilizing aid. Subsequently any remaining
balance of water, if any should be required, is then added. Any pH adjusting
agents
and/or pH buffering compositions are desirably added last to be in a
sufficient amount
in order to bring the formed composition within the pH range desired.
The compositions according to the invention may be conveniently applied to a
substrate in any of a variety of conventional fashions, such as by spraying;
dipping,
coating, padding, foam or roller application, or by a combination of one or
more of
these, or with other methods not noted here but known to the art. The
compositions
according to the invention are used in a conventional manner in the cleaning
of carpet
surfaces. Generally, carpets are effectively cleaned by spraying about 5 grams
per
square foot of the carpeted surface with the aqueous cleaning composition and
subsequently allowing said composition to penetrate among the carpet surface
and the
fibers. Desirably, this is further facilitated by the use of a manual
agitation action,
such as by rubbing an area of the carpet to be treated with a device such as a
brush,
sponge, mop, cloth, non-woven cloth, and the like until the aqueous
composition is
well intermixed amongst the carpet fibers. Subsequently, the treated area is
permitted
to dry, which usually requires from as little as 5-10 minutes in areas of high
heat and
low humidity to as much as an hour or more in poorly heated and high humid
locations. Generally, however, the drying period under typical conditions is
between
about 15 minutes to about 30 minutes. Optionally, but desirably, any remaining
composition may be removed from the carpet such as by vacuuming in a
conventional
manner. In a further optional technique, the carpet may be brushed so to
remove any
residue of the aqueous composition from amongst the carpet fibers, and then
vacuumed or brushed out from the carpeted area.
In contrast to many of the compositions known in the prior art, the aqueous
compositions according to the present invention provide surprisingly good
cleaning
efficacy, and simultaneously a surprisingly effective anti-recoiling
characteristic to the
-- 20 --
CA 02278026 1999-07-15
WO 98/31T16 PCT/US97/19217
treated carpet surface. Thus, the compositions of the present invention
provide
surprisingly provide these desirable benefits using low cost and widely
available
materials, frequently without the necessary inclusion of costlier known-art
anti-
resoiling agents or with such costlier materials in smaller amounts.
The following examples illustrate the superior properties of the formulations
of the invention and particular preferred embodiments of the inventive
compositions.
The terms "parts by weight" or "percentage weight" are used interchangeably in
the
specification and in the following Examples wherein the weight percentages of
each
of the individual constituents are indicated in weight percent based on the
total weight
of the composition, unless indicated otherwise.
The following examples illustrate the superior properties of the formulations
of the invention and particular preferred embodiments of the inventive
compositions.
Exemplary formulations illustrated on Table 1 indicate the weight percentages
of each
of the individual constituents based on the total weight of the composition of
which it
forms a part.
The example formulations described in more particular detail on Table 1
below were prepared in accordance with the following general protocol. To a
mixing
vessel (glass beaker equipped with a magnetic stirrer) was first provided a
part of the
total amount of water, the agitator was then energized, and to the water was
then
added the remaining constituents. The order of the addition of the remaining
constituents varied from formulation to formulation as the order of addition
is not
critical, but the addition of surface active agents first to the water was
generally done
as aiding in the dissolution/dispersion of the remaining constituents. The
contents of
the mixing vessel were well mixed, and ultimately the remaining balance of
water, if
any was required, was then added. These example formulations were used "as
prepared", that is to say without further dilution in the subsequent testing
protocols.
Examples which fall within the scope of the invention are denoted as "Ex.",
while "comparative" examples are prefixed with "C".
-- 21 --
CA 02278026 1999-07-15
wo ~m~6 rcz'ms9~n~m
TABLE 1 _ _
~~
Formulation: C1 C2 C3 Ex.1 Ex.2 Ex.3 Ex.4
tetrasodium EDTA -- -- -- 2.5 2.5 5.0 6.0
(38%)
fluorochemical salt-- -- 0.4 0.4 -- -- --
(30%)
sodium lauryl sulfate4.0 4.0 4.0 4.0 4.0 4.0 4.0
(30%)
ethylene glycol 1.0 1.0 1.0 1.0 1.0 1.0 1.0
monohexyl
ether
alkoxyiated alcohol-- 0.25 0.25 0.25 0.25 0.25 0.25
isopropanol 2.0 2.0 2.0 2.0 2.0 2.0 2.0
fragrance 0.2 0.2 0.2 0.2 0.2 0.2 0.2
preservative (1.5%)0.05 0.05 0.05 0.05 0.05 0.05 0.05
citric acid 0.01 0.01 0.01 0.01 0.25 0.57 --
sulfuric acid (20%)-- -- -- -- -- -- 2.43
DI water 92.7492.49 92.09 89.5989.75 86.9584.07
The identity of the individual constituents used to produce the formulations
of Table I
are indicated on Table 2, below. The amounts in Table 1 are on an "as is"
basis as
supplied by the respective supplier. The weight percentages of "actives" in a
respective constituent are indicated on Table 2, below.
TABLE 2
tetrasodium EDTA Hampene~ 100 (Hampshire Chemical
(38%) actives_.................._._.~...
__._...~~--_.. _
~
~
3g/
!!~_
C
:
_...~._ ..
fluorochemical .
salt ._
_
._
__
.
ZONYL~ 7950 (EI DuPont de Nemours))
30% 30%wt..,.actives
( ) '
.__......_._._..___.~_...._-.__-___-___..____....
-~._ ....
sodium lauryl Rhodapon~ LCP (Rhone-Poulenc Co.,
sulfate
(30%) Princeton NJ). 30%wt. actives_
~
~!. ,_, _
_ (lJnion Carbide
ethylene glycol r ~Hexyl CELLOSOLVE~
monohexyl ether -. _ Corp., Danbu_ ry CT) _ _
__._Y _..-__ _,~-
~
alkoxylated alcoholPolyTergent SL-55~ (Olin Chemical
Co.)
~
_-._ Stamford CT) _
__._...__.._~......
___
...
;_.
-
__
.. ~
_Isopropanol _,._,-_~
'sopropanol_-
_ ~~__._._.__
~.~_- ~._. .
g ,~,._.. - pro ...rietar , com osition
Fra ra nce _....__._..._._p .._..........Y.._...
..__.....p ..._._._ ___ _.__._...._..-_~._
_._.__._....____~.
preservative (1.5%)Kathon~ CGIICP (Rohm & Haas Co.,
_ Philadelphia P_A), 1.5_/ activesT.,~~_._-__T
citric acid ~ anhydrous citric acid _ __
_.__ _..__.u...
~.~
~-
T
~~~
_. _ } _.~_ ___._._......._._....__........_._.....
sulfuric acid _.__._.__._.____..._.._
(20% _,_. .
es
_
__
_.aqueous.,sulfuric-acid,,.20%wt.
activ
DI water deionized water
The formulations denoted on Table 1 above were tested for their general
cleaning and anti-resoiling behaviour on standardized carpet substrates in
accordance
with two tests, "Jar Mill" and "Hallway" tests. In both of these tests carpet
swatches
-- 22 --
082951249W01 CA 02278026 1999-07-15
made of a medium pile density light beige colored level loop nylon carpeting
were used
as a standard testing substrate. Such carpet swatches are similar to those
presently
commercially available as DuPont Stainmaster~ carpets from a variety of
commercial
sources. Such carpet swatches were used as standard testing substrates in the
following
evaluations of cleaning and anti-resoiling as further described below.
From the tested carpet swatches, reflectance was evaluated utilizing a Gardner
Colorimeter, using an "LAB color scale". These results were used to provide a
quantitative means for light reflectance, which was a useful measure of anti-
recoiling
behaviour of a tested formulation. These results were also evaluated against a
carpet
surface which was untreated by any composition, and is indicated as a
"control(untreated)" in the following tables.
The Jar Mill test was generally in accordance with the AATCC Test Method 123-
1989 for "Carpet Soiling: Accelerated Soiling Method" as published in the
AATCC
Technical Manual, published 1992.
The Jar Mill test was performed three times using different formulations; the
identity of these particular formulations is denoted on Table 3, following.
In each one of the tests there was used a different test carpet swatch as
described
above having a length of approximately 23 inches (58.5 cm) and a width of
approximately 6 inches ( 15.25 cm). These test carpet swatches were divided
into
successive zones, each zone having a width of 6 inches ( 15.25cm) and
occupying
portions along the length of the carpet swatch. The zones, were ordered in
numerical
succession beginning at one end of the carpet swatch and continuing in
contiguous zones
to the opposite end of the carpet swatch. Specifically, zone 1 which was
contiguous with
one end of the carpet swatch, had a width of 6 inches ( 15.25 cm) and a length
of 4 inches
( 10.5 cm), thus providing a test carpet surface area of 24 square inches (
160 square cm).
The next contiguous zone was zone 2 being 6 inches ( 15.25 cm) in width and 3
inches
(7.6 cm) in length, providing a test carpet surface area of 18 square inches
(116 square
cm). The third zone, contiguous with the end of the second zone was 6 inches
(15.25 cm)
in width and 3 inches (7.6 cm) in length, thus again providing a test carpet
surface area of
18 square inches ( 116 square cm) . The next, zone 4 was contiguous to zone 3
and had a
width of 6
-- 23 --
,0.r'~IEND~ED SHEET
I~EA/c?
08295I249W01
CA 02278026 1999-07-15
inches ( 15.25 cm) and a length of 3 inches (7.6 cm), again providing a test
carpet surface
area of 18 square inches ( 1 I 6 square cm). The next zone, zone 5, was
contiguous to the
prior zone 4, was 6 inches ( 15.25 cm) in width and also 3 inches ( 15.25 cm)
in length and
this provided a test carpet surface area of 18 square inches ( I 16 square
cm). The next
succeeding zone, zone 6, had a width of 6 inches ( I 5.25 cm) and a length of
3 inches (7.6
cm), providing a test carpet surface area of 18 square inches ( 116 square
cm). The final
zone, which occupied the remaining portion of the carpet test swatch, and was
contiguous
to zone 6, was 6 inches in width ( 15.25 cm), and occupied the remaining 4
inches ( 10.5
cm) in length of the carpet test swatch and is designated as zone 7. This zone
7 provided
a carpet test area of 24 square inches ( 160 square cm).
In accordance with Test 1, to zone 2, as described above, was applied
approximately 3.65 grams of Formulation C2. Similarly to zone 4 was applied
approximately3.65 grams of formulation according to C3, and in a like manner
approximately 3.65 grams of the formulation according to Example 1 was applied
to
zone 6. Thereafter, each of these zones of the carpet test swatch were rubbed
into the
carpet utilizing 20 transverse strokes and 20 longitudinal strokes which were
manually
applied in a uniform manner utilizing a clean folded laboratory non-woven wipe
(KIMWIPE~ Kimberly Clark Corporation). The carpet test swatch was then
permitted to dry overnight.
The next day, the treated test carpet swatch was then subj ected to the AATCC
Test Method 123-1989 wherein the carpet swatch was tumbled with a prepared
synthetic soil for an established period of time. This synthetic soil
comprised the
following: 28% by weight peat moss; 17% by weight Portland cement; 17% by
weight Kaolin clay; 17% by weight silica (200 mesh); 1.75% by weight carbon
black
(lamp or furnace black); 0.50% by weight red iron oxide; and 8.75% by weight
of
medicinal grade mineral oil. This synthetic soil was prepared in accordance
with the
recited AATCC Test Method.
The carpet swatches were then placed into porcelain ball mill jars and tumbled
with specimens of the synthetic prepared soil as well as flint pebbles for a
time.
interval of 5 minutes, after which the test carpet swatch was removed.
Subsequently,
the test carpet swatch was cleaned by light vacuuming with a tank type vacuum
cleaner in accordance with the AATCC test protocols.
-- 24 --
/-~,i~l~~.~r-~,,~~ ~~-"CT
ir;'~;-.~~
CA 02278026 1999-07-15
WO 98/31776 PCT/US97I19217
Subsequently, the test carpet swatch was evaluated for light reflectance
utilizing a BYK Gardener Spectrophotometer/Colorimeter set on "D65"
illumination.
Nine readings were taken of each zone of the test carpet swatch, and the mean
value
for "L" as reported by the BYK device. This reading indicates the "lightness"
or
S "darkness". of an evaluated sample, which provided the most relevant data
with
respect to the level of the anti-resoiling properties of a test formulation.
These
readings are reported in Table 3.
Similarly, the protocol outlined above was repeated for test 2, except that in
zone 2 was applied approximately 3.65 grams of the Formulation of C2, to zone
4 was
applied approximately 3.G5 grams of the formulation of Example 2, and to zone
6 was
applied approximately 3.G5 grams of formulation according to Example 3. All
other
portions of the tests were performed in substantially the same manner as
described
above with reference to Test 1. The percent reflectance, as obtained from the
BYK
1 Gardener Spectrophotometer/Colorimeter, is similarly reported on Table 3.
Similarly, the same general protocol as performed for test 1 was also utilized
in performing Test 3. However, in test 3, approximately 3.G5 grams of the
formulation according to C 1 was applied to zone 2, approximately 3.65 grams
according to C2 were applied to zone 4, and approximately 3.65 grams of the
formulation according to Example 4 were applied to zone 6 of the standard
carpet
swatch. Again, the results as obtained from the measurements utilizing the BYK
Gardener Spectrophotometer/ Colorimeter are reported on Table 3.
As may be seen from the results reported for Test 1, the formulation according
to C2 contained no fluorochemical and no EDTA constituent, and also
demonstrated
the poorest anti-resoiling properties. The formulation according to C3
including a
fluorochemical constituent, and showed a slight increase in the anti-resoiling
properties. Surprisingly, however, the addition of the amounts of EDTA salt,
further
in conjunction with the fluorochemical as illustrated in Example l, provided a
substantial increase in the anti-resoiling properties which is both better
than the
formulation according to C3 as well as better than the control (untreated)
test carpet
swatch.
-- 25 --
CA 02278026 1999-07-15
WO 98131'Tl6 PCT/US97/19Z17
Turning now to the results reported in conjunction with Test 2, each of the
formulations in Test 2 contained no fluorochemical constituent. As may be seen
from
the results, the formulation according to C2 contained no fluorochemical and
no
EDTA salt and showed poor anti-resoiling properties. The next formulation
according
to Example 2 contained a small amount of EDTA salts, and demonstrates similar
anti-
resoiling properties to that of C2. Again, surprisingly the addition of higher
amounts
of EDTA salts to the formulation, as is demonstrated by Example 3 of Test 2,
shows a
significant and surprising improvement in the anti-resoiling properties. It
was also
observed that the controlled (untreated) test carpet swatch demonstrated
excellent
anti-resoiling characteristics. This can in part be attributed to the fact
that the
controlled (untreated) test carpet swatches were not provided with any liquid
chemical
compositions, such as formulations of Table 1, and thus would have a minimal
or
negligible effect on attracting soil to their untreated surfaces.
With respect now to the results reported for Test 3, the first formulation
I 5 according to C 1 included no nonionic surfactant constituent, no
fluorochemical
constituents, and no EDTA salts and yet provided a good amount of anti-
recoiling
characteristics to the carpet surface. The absence of certain constituents,
especially
the nonionic surfactants which are known to the art to be sticky and tacky
good
attractors and retainers of soil particles, are absent from the formulation
according to
C 1. Turning now to the formulation according to C2, this formulation included
nonionic surfactants, and a concomitant decrease in the anti-resoiling
properties of the
test carpet swatch are observed. Turning now to the remaining formulation
according
to Example 4 which included a significant amount of EDTA salts as well as the
same
amount of the nonionic surfactant according to.C2. Surprisingly, a striking
improvement in the anti-resoiling properties, notwithstanding the relatively
high
amounts of the nonionic surfactant constituent, were achieved. Further, the
results
obtained with use of formulation of Example 4, were favorably comparable to
that of
the control (untreated) portion of the test carpet swatch. It was also noted
that in
Example 4, the increased amount of citric acid was provided as a pH adjusting
agent.
-- 26 --
08295/249W01 CA 02278026 1999-07-15
TABLE 3
Test Formulation % Reflectance
1 C2 51.67
C3 54.38
Ex.1 60.44
Control (untreated) 59.66
2 C2 54.56
Ex.2 54.11
Ex.3 57.94
Control (untreated) 61.82
3 C1 60.49
C2 57.28
Ex.4 60.38
Control (untreated) 61.81
Hallwa"LTest:
A test designed to be more representative of the results, of a more
characteristic
setting for a carpet was performed. In this test, a test carpet swatch,
treated with several
of the formulations noted in Table 1 was installed in a busy hallway for a
period of time.
The carpet swatch was of the DuPont Stainmaster~ carpet type described above,
and
measured 3 feet in width and 7 feet in length. This carpet swatch was divided
into five
zones, the first Zone 1 beginning at one end and being 3 feet in width and 2
feet in
length. Zone 2 being contiguous to the prior zone 1 and being 3 feet (0.9
metres) in
width and extended for 1 foot (0.3 m) in length. The next contiguous zone,
Zone 3, 3 feet
(0.9 m) in width and extending 1 (0.3 m) foot in length. Zone 4, contiguous to
the prior
Zone 3, 3 feet (0.9 m) in width and 1 foot (0.3 m) in length. The final Zone
5, being the
remaining 2 feet (0.6 m) in length of the test carpet swatch and 3 feet (0.9
m) in width.
This test carpet swatch was treated in accordance with the following protocol:
Zone 1
and Zone 5 were left untreated and are designated "control (untreated)", and
were used as
a comparative example. To Zone 2 was applied approximately 50 grams of the
formulation according to C 1, as described in detail in Table 1 above. To Zone
3 was
applied 50 grams of Formulation C2 of Table 1, and to Zone 4 was applied 50
grams of
the formulation according to Example 4, each of which are described in Table 1
above.
Thereafter, each of these formulations were rubbed into their respective zones
of the
carpet utilizing 20 transverse strokes and 20 longitudinal strokes. Rubbing
was manually
applied in a uniform manner utilizing a clean folded laboratory non-woven wipe
(KIMWIPE~, Kimberly Clark Corporation). The carpet test swatch was then
permitted
to dry overnight.
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CA 02278026 1999-07-15
WO 98/31'176 PCT/U897/19217
The thus treated test carpet swatch was installed in the hallway, and taped
down using a strong adhesive tape at its edges. The carpet was retained in
this
location for four weeks, and the normal passerbys of the hallway were
permitted to
pass over the total surface of the thus installed test carpet swatch. It was
estimated
that approximately 16,000 individuals passed across the surface of the test
carpet
swatch during this four-week interval. Subsequently, the test carpet swatch
was
removed from the floor, and each of the zones was evaluated utilizing the BYK
Gardener Spectrophotometer/Colorimeter set for D65 illumination as described
above
with reference to the Jar Mill testing. As therein, nine readings were taken
on each of
the zones, and the mean value of these are reported on Table 4, below.
TABLE 4
Test Formulation % Reflectance
4 ~ C1 79.84
C2 79.14
Ex.4 79.95
As can be
seen by
the results
reported
on Table
4, the formulation
according
to
C 1 included no nonionic constituent, no fluorochemical constituent and no
EDTA
salts. The formulation according to C2 included a nonionic surfactant
constituent, no
fluorocarbon constituent and no EDTA salt in its make up. As can be seen, its
1 S reported percentage light reflectance was somewhat inferior to that of the
prior
sample.
Surprisingly; the formulation according to Example 4 which included no
fluorochemicai, but did include a higher amount of EDTA salts provided
significantly
improved results, with the highest reflectance of reading of any of the tested
areas of
the test carpet substrate in this test, text No. 4. Thus, it can be seen that
notwithstanding the increased amounts of the nonionic surfactant, the addition
of the
greater amounts of the tetra sodium EDTA salts to the compositions of Example
4
provided a significant improvement to the overall anti-resoiling properties of
the
formulation, which were better than the formulation according to C l, as well
as the
_ nonionic surfactant containing formulation of C2.
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