Note: Descriptions are shown in the official language in which they were submitted.
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TEXTILES TREATED WITH
HYPERBRANCHED POLYETHYLENEIMINE DERIVATIVES
FOR ODOR CONTROL PROPERTIES
TECHNICAL FIELD
The present disclosure is directed to the field of hyperbranched
polyethyleneimine derivatives useful for treating textile substrates. More
specifically, this disclosure relates to treatments used to provide wash-
durable
odor control in textiles, particularly in synthetic or synthetic-containing
textile
substrates. The chemical treatment also reduces wrinkling and imparts softness
and moisture wicking to the treated textile.
The present disclosure is directed to a molecule having a hyperbranched
polyethyleneimine core to which is attached, at a minimum, one or more
hydrocarbon groups. Optionally, linking compounds may connect the
hydrocarbon groups to the hyperbranched polyethyleneimine core. Additionally,
other organic compounds may also be used to "cap" the branches of the
hyperbranched polyethyleneimine that are unreacted with hydrocarbon groups.
In one embodiment, the hydrocarbon groups comprise up to 20% of the weight
of the hyperbranched polyethyleneimine derivative. In such embodiment, the
resulting treated textile exhibits wicking properties that are desired for
textiles
used in apparel and other applications. To produce a treated textile whose
finish
is capable of withstanding multiple launderings, it is preferable to use a
cross-
linking agent or compound to secure the hyperbranced polyethyleneimine
derivative to the textile surface.
In a second embodiment, the hydrocarbon groups comprise up between about
20% and about 80% of the weight of the hyperbranched polyethyleneimine
derivative. In such embodiment, it has been found that durability may be
achieved without the use of a separate cross-linking agent or compound,
although one may be incorporated if so desired for certain applications.
Textiles
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treated with derivatives having a greater amount of hydrocarbon groups tend to
exhibit finishes that are more water-repellent, which may be useful in some
circumstances.
BACKGROUND
It has long been desirable to produce a textile substrate having durable odor
adsorption capabilities. In particular, the abatement of human sweat odors is
useful in a variety of different applications. For instance, hunters are
interested
in preventing their body odors from reaching animals being pursued. In perhaps
a more common application, apparel that may be worn several times before
requiring laundering would provide considerable benefits to users thereof.
Manufacturers have used a variety of approaches to solve the problem of odor
abatement. A first approach is the treatment of the textile article with
antimicrobial compounds or the incorporation of antimicrobial compounds into
the yarns used to make the substrate. Antimicrobial-treated textiles function
to
reduce odors by controlling or preventing the growth of microorganisms. When
microorganisms grow, they degrade materials into volatile organic compounds,
which are often malodorous. While preventing the growth of microorganisms,
approaches using antimicrobials fail to address the issue of odor control once
volatile organic compounds are present in the textile.
Another approach to the problem of odor control is to incorporate carbon black
particles, granules, fibers, or cloths into a textile. Depending on the chosen
pore
size and source material, carbon black is generally effective at adsorbing
odors
when dry, but it tends to lose some of its efficacy when wet (as the surface
area
becomes blocked by water or other aqueous contaminants). A second problem
with carbon black is that it must be bound to the textile by adhesives or
other
binders, often reducing the breathability of the treated textile. Finally,
carbon
black imparts a black color to the textile surface being treated, which is
unsuitable in many situations (for example, with light-colored apparel).
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Other particles, such as zeolites, have also been used for textile odor
reduction.
Many of these exhibit the same problems associated with carbon black, while
being functionally less effective.
More recently, manufacturers have used cyclodextrins and cyclodextrin
derivatives in an effort to produce odor-reducing textiles. However, as will
be
demonstrated herein, cyclodextrins are not particularly efficacious in
reducing
odors associated with human sweat, nor are they particularly durable to
repeated
launderings.
Thus, a need exists for a wash-durable odor abatement chemistry that
preferably
imparts benefits such as wrinkle resistance, moisture wicking, and softness.
The
present treatment provides a solution to such needs providing a specific
hyperbranched polyethyleneimine structure, which is linked to one or more
hydrocarbon groups having linear portions of between 5 and 30 carbon atoms
and which may additionally be linked to one or more organic "capping"
compounds.
SUMMARY
This disclosure is directed to treatments for synthetic textile goods that
impart
odor control properties to the treated textiles. Additionally, the chemical
treatment provides benefits in terms of reduced drying time, reduced
wrinkling,
and, in some circumstances, improved moisture wicking.
The present treatment comprises a modified hyperbranched polyethyleneimine
compound, also referred to herein as a "hyperbranched polyethyleneimine
derivative." The hyperbranched polyethyleneimine derivative comprises at least
one hyperbranched polyethyleneimine (a "hydrophilic component") that has been
linked to one or more hydrocarbon groups having between 5 and 30 carbon
atoms linearly arranged ("hydrophobic component(s)", which may be linked to
the hyperbranched polyethyleneimine using any of a number of different
linkages). In another embodiment, the chemical treatment also comprises one
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or more additional organic "cap" compounds attached to the hyperbranched
polyethyleneimine core.
Preferably, the hydrophobic components (that is, hydrocarbon groups and
optional linking compounds) are electrophilic, so that they react with the
nucleophilic hyperbranched polyethyleneimine molecule. Any of a number of
acceptable linking groups may be used to link the hydrocarbon groups to the
hyperbranched polyethyleneimine, as will be described herein, or the
hydrocarbon groups may link directly to the hyperbranched polyethyleneimine
molecule.
In one embodiment, the hydrocarbon groups comprise up to 20% of the weight
of the hyperbranched polyethyleneimine derivative. In such embodiment, the
resulting treated textile exhibits wicking properties that are desired for
textiles
used in apparel and other applications. To produce a treated textile whose
finish
is capable of withstanding multiple launderings, it is preferable to use a
cross-
linking agent or compound to secure the hyperbranced polyethyleneimine
derivative to the textile surface.
In a second embodiment, the hydrocarbon groups comprise up between about
20% and about 80% of the weight of the hyperbranched polyethyleneimine
derivative. In such embodiment, it has been found that durability may be
achieved without the use of a separate cross-linking agent or compound,
although one may be incorporated if so desired for certain applications.
Textiles
treated with derivatives having a greater amount of hydrocarbon groups tend to
exhibit finishes that are more water-repellent, which may be useful in some
circumstances.
The disclosure is further directed to the process for treating textiles with
the
present chemical treatment, wherein the chemical treatment is applied to at
least
a portion of the fiber, yarn, textile, or composite. In a presently preferred
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embodiment, the target fabric is placed into the chemical treatment (e.g, by
dipping), then padded and dried in a single continuous process.
This disclosure is further directed to the fibers, yarns, fabrics, textiles,
finished
goods, or nonwovens (encompassed herein under the terms "textiles" and
"webs") treated with the subject hyperbranched polyethyleneimine derivatives.
Such textiles and webs exhibit greatly improved odor control properties, even
after multiple launderings. Further, such treated textiles also exhibit
enhanced
moisture wicking and reduced wrinkling and drying time.
DETAILED DESCRIPTION
The present chemical treatment is especially well-suited for use with
synthetic
substrates. The term "synthetic" refers to any man-made fiber type, including,
without limitation, polyester, polyamide (e.g., nylon), acrylic, polyethylene,
polypropylene, aramids (e.g., NOMEX and KEVLAR ) and the like.
Preferably, the substrate comprises a majority of synthetic content and may
include a combination of synthetic fiber types or a combination of synthetic
and
natural fiber types.
Of principal utility in the present chemical treatment is the hyperbranched
polyethyleneimine (h-PEI) molecule, which may also be referred to herein as
the
hydrophilic component of the compound. In schematic terms, the h-PEI
molecule can be described as having a central core surrounded by a plurality
of
molecular branches, with each branch projecting outward from the core and
having a highly reactive end group. It is to be expected that partial linkage
of the
branches to themselves often occurs. The molecule typically exhibits a very
high
charge density per area, meaning that there are a high number of positive
charges clustered densely together around the molecular core. This
configuration makes the molecule very capable of interacting with a wide range
of other molecules, many of which will be described herein. The number of
molecules that may be attached to the h-PEI molecule depends on the number
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average molecular weight (Mõ) of the h-PEI, which reflects the number of
branches available for attachment.
For the applications that are contemplated herein, hyperbranched
polyethyleneimines having a number average molecular weight (Mõ) of between
about 300 and about 2 million are preferred, with Mõ of between about 1,000
and
about 75,000 being more preferred.
To the h-PEI molecule are attached at least one, and preferably more than one,
hydrocarbon groups to increase the hydrophobicity of the resulting compound
(i.e., the h-PEI derivative). These hydrocarbon groups, together with any
linking
compounds which may be used to attach them to the h-PEI molecule, are
collectively referred to as the "hydrophobic components" of the dye-reactive
molecule. These hydrocarbon groups may be linear molecules or may contain
branched or aromatic portions, which have an electrophilic group capable of
reacting with the nucleophilic h-PEI. Preferably, regardless of the structure
of
the hydrocarbon, the linear portion of the hydrocarbon group contains between
about 5 and about 30 carbon atoms and, more preferably, contains between
about 10 and about 24 carbon atoms. Mixtures of various length hydrocarbons
may also be used.
Examples of electrophilic hydrocarbons include, without limitation, carboxylic
acids, ketene dimers, formates, acetyl halides (such as acetyl chloride),
esters,
anhydrides, alkyl halides, epoxides, isocyanates, and the like. Preferred
examples include stearic acid, hydroxy stearic acid, isostearic acid, and
palmitic
acid.
In a first embodiment, the weight ratio of h-PEI to hydrophobic groups is from
about 1000:1 to about 5:1 and, more preferably, is from about 100:1 to about
10:1. In a second embodiment, the weight ratio of h-PEI to hydrophobic groups
is from about 5:1 to about 1:10 and, more preferably, is from about 2:1 to
about
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1:5, depending on the Mõ of the h-PEI. Most preferably, weight ratios of h-PEI
to
hydrophobic group from about 1:1 to about 1:4 are used.
The present h-PEI derivatives possess the structure shown below:
(R),r h-PEI - (A)y
where R is a non-hyperbranched hydrocarbon group (for example, such as alkyl,
alkenyl, arylalkyl, and arylalkenyl groups, where the number of carbon atoms
in
the linear portion of the hydrocarbon is between 5 and 30 carbon atoms), where
x is a number from 1 to about 10,000 (depending on the Mõ of the h-PEI), where
h-PEI is a hyperbranched polyethyleneimine, where A is a small organic
"capping" compound, where y is a number from 0 to 500,and wherein R is
present in an approximate amount of between about 0.1% and about 80% by
weight of the molecule.
It is understood that, in the synthesis of molecules such as those fitting the
general structure provided above, the actual product exhibits a polydispersity
(a
distribution of ratios) and the molar ratio of each molecule will vary
somewhat
around the target ratio.
Optionally, small organic molecules (generically shown as "A" in the structure
above) may be used to "cap" the unreacted branches of the hyperbranched
polyethyleneimine. Generally speaking, the capping molecule "A" has from one
to four carbon atoms. Any caps that will react with the amine (NH or NH2)
portion of the h-PEI molecule may be used, including, without limitation,
epoxides, anhydrides, esters, acids, carbonates, sulfates, formates,
isocyanates,
and mixtures thereof. Specific examples of such caps include, without
limitation,
ethylene oxide, propylene oxide, methyl bromide, acetic acid, vinyl
sulfonates,
trifluoroacetic acid, and succinic anhydride. Mixtures of different "cap"
molecules
may be used.
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Ethylene oxide (EO) or propylene oxide (PO) chains are especially useful as
capping compounds in the present treatment to prevent the treated substrate
from yellowing when exposed to high manufacturing temperatures (for example,
temperatures greater than 350 F). The addition of such chains is not required
to achieve odor control and other benefits of the present treatment, but
merely to
impart additional benefits. For example, it has been found that the addition
of
EO or PO chains within the h-PEI derivative improves moisture wicking and
produces softness in the treated substrate.
One potentially preferred "R" group has a C17H35 structure, which in the above
structure forms a stearic amide. When using this R group and an h-PEI having
an Mõ of 1200, representative molar ratios of h-PEI to R are 1:2, 1:4, 1:6,
1:8,
1:10, and 1:12. Similarly, when the Mõ of the h-PEI molecule is about 10,000,
representative molar ratios of h-PEI to R are 1:25, 1:60, 1:80, and 1:100.
Finally,
when the Mõ of the h-PEI molecule is about 75,000, representative molar ratios
of h-PEI to R are 1:400, 1:500, and 1:600.
The chemical synthesis of the present treatment molecules is conducted by
reacting the h-PEI molecule with a hydrophobic R-containing electrophilic
molecule in the presence of nitrogen. It has been found that mechanical
agitation of the reagents in a vessel under nitrogen at a temperature of about
150 C produces the h-PEI derivatives described herein. The time necessary to
complete the reaction depends on the amount of reagents that are being reacted
and the size of the reaction vessel. The resulting compounds, referred to
herein
as "h-PEI derivatives", are typically in the form of an oily liquid or waxy
solid.
In one preferred embodiment, h-PEI derivatives have hydrophobic agents
present in an amount of at least 0.1 % to up to about 20% of the weight of the
h-
PEI derivative, and more preferably, from about 2% to about 15% of the weight
of the h-PEI derivative. In an alternate embodiment, h-PEI derivatives have
hydrophobic agents present in an amount of at least 20% to about 80% of the
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weight of the h-PEI derivative, and more preferably, from about 30% to about
75% of the weight of the h-PEI derivative.
To prepare a treatment bath for textiles using the h-PEI derivatives described
herein, one approach is to heat the h-PEI derivative to its melting point, so
that it
may be poured into a vessel where it is combined, via high speed and high
shear
agitation, with hot water. In this instance, the phrase "hot water" refers to
water
having a temperature equal to or greater than the melting point of the h-PEI
derivative. Suitable equipment for achieving high speed and high shear
agitation
includes propeller-type mixers, Jago -type agitators, homogenizers, roll mill,
ball
mill, microfluidization, and the like.
The dispersion that results from the forcible introduction of the h-PEI
derivative
into water may be assisted and stabilized by addition of a solubilizing agent
(e.g.,
an acid or a surfactant), the amount of which depends on the molecular weight
of
the h-PEI and the molar ratio of h-PEI to hydrophobic components. Acetic acid
is one potentially preferred acid for this purpose (excess acid being
evaporated
off during subsequent drying of the treated textile substrate). Amounts of
greater
than 0.1 % acid, by weight of solution, may be used successfully. Preferably,
the
amount of acid will be in the range of about 0.1% to about 50% of the weight
of
the h-PEI derivative.
The fiber, the yarn, the fabric, or the finished garment may be dyed using
conventional processing, after which it is exposed (by methods known in the
art
such as by soaking, spraying, dipping, padding, foaming, exhausting, and the
like) to the aqueous dispersion of the treatment chemistry. In some instances,
it
may be possible to introduce the treatment' chemistry onto a garment by
replacing the softening chemistry (normally applied during the laundering
process) with the treatment described herein. Alternately, the treatment
chemistry may be applied to a greige (undyed) textile, if the textile is to be
used
in its undyed state.
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The treated web is then removed from the solution and dried, preferably at
temperatures between room temperature and 400 F, and more preferably, at
temperatures between about 100 F to about 380 F. The typical add-on weight
of the h-PEI derivative is from about 0.1% of the weight of the fabric to
about
10% of the weight of the fabric and, preferably, is from about 0.2% of the
weight
of the fabric to about 5% of the weight of the fabric.
The treated substrates exhibit durable odor control, even after multiple
launderings. Additionally, and surprisingly, the substrates also have durable
softness, reduced wrinkling after laundering / drying, and improved moisture
wicking capability.
Without wishing to be bound by theory, it is hypothesized that the h-PEI
derivatives disclosed herein possess a molecular configuration that
facilitates
odor adsorption. Specifically, the h-PEI derivatives have a hydrophilic core
surrounded by a hydrophobic "shell" that is formed by the plurality of
hydrocarbon groups attached to the core h-PEI molecule. Such a configuration
results in numerous voids within the derivative molecule, in which volatile
odor
molecules having different polarities may be trapped. Additionally, secondary
interactions-such as, for example, Van der Waals forces, hydrogen bonding,
and ionic interactions-may also contribute to the odor-trapping ability
exhibited
by textiles treated with the present derivatives.
In one embodiment (particularly when the hydrocarbon groups are present in an
amount of between 0.1% and 20% of the weight of the h-PEI derivative), a
separate cross-linking agent is incorporated into the aqueous solution or
dispersion to enhance treatment durability. Suitable cross-linking agents for
this
purpose include epoxides, chlorotriazines and their derivatives, azetidines,
blocked isocyanates, and melamine derivatives, which may further enhance the
durability of the treatment chemistry. When used, the cross-linking agent is
preferably present in an amount of between about 0.05% and about 5% of the
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weight of the treated textile. Preferably, the ratio of h-PEI derivative to
cross-
linking agent is from about 1:0.1 to 1:1.
Other finishing agents may also be used, such as wetting agents, softeners,
soil
release agents, flame retardants, and the like.
In order to further illustrate the present derivatives and advantages thereof,
the
following specific examples are given, it being understood that the same are
intended only as illustrative and are in no way limiting.
COMPARATIVE EXAMPLE A
A 100% polyester knit fabric was used as the substrate for Comparative
Example A. A treatment solution was created, which contained 7.5% (by weight)
of a hydroxypropyl beta-cyclodextrin (available from Wacker Chemical under the
tradename CAVATEX W7 HPTL) and 2.0% (by weight) of a blocked isocyanate
cross-linking agent (available from Clariant Corporation under the tradename
ARKOPHOBO DAN). The knit fabric was dipped into the treatment solution and
padded at a pressure of 40 p.s.i. to remove excess treatment solution. The
treated fabric was then dried at about 370 F for about 3 minutes (until dry).
COMPARATIVE EXAMPLE B
'A woven fabric containing 52% nylon by weight and 48% cotton by weight was
used as the substrate for Comparative Example B. For this Comparative
Example, the fabric was dipped into a bath containing only water and then
padded at a pressure of about 40 p.s.i. to remove excess water. The fabric was
then dried at about 310 F for about 10 minutes (until dry).
COMPARATIVE EXAMPLE C
The fabric from Comparative Example B was used in Comparative Example C.
For this Comparative Example, the fabric was dipped into a bath that contained
7.5% (by weight) of a hydroxypropyl beta-cyclodextrin (available from Wacker
Chemical under the tradename CAVATEX W7 HPTL) and 2.0% (by weight) of
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a blocked isocyanate cross-linking agent (available from Clariant Corporation
under the tradename ARKOPHOB DAN) and then padded at a pressure of
about 40 p.s.i. to remove excess. The treatment solution used in Comparative
Example C was the same as that used in Comparative Example A. The fabric
was dried at about 310 F for about 10 minutes (until dry).
COMPARATIVE EXAMPLE D
The fabric from Comparative Example B was used in Comparative Example D.
For this Comparative Example, the fabric was dipped into a bath that contained
about 5.0% (by weight) of a melamine-based repellent material (available from
Ciba Specialty Chemical under the tradename PHOBOTEX JVA) and 2.0% (by
weight) of a blocked isocyanate cross-linking agent (available from Clariant
Corporation under the tradename ARKOPHOBO DAN). The fabric was then
padded at a pressure of about 40 p.s.i. to remove excess, after which the
fabric
was dried at about 310 F for about 10 minutes (until dry).
COMPARATIVE EXAMPLE E
A woven fabric containing 52% nylon by weight and 48% cotton by weight was
used as the substrate for Comparative Example E. The fabric was dipped into a
bath that contained about 6.0% (by weight) of a hydroxypropyl beta-
cyclodextrin
(available from Wacker Chemical under the tradename CAVATEXO W7 HPTL)
and 1.0% (by weight) of a blocked isocyanate cross-linking agent (available
from
Clariant Corporation under the tradename ARKOPHOB DAN) and then padded
at a pressure of about 40 p.s.i. to remove excess. The fabric was then dried
at
about 330 F for about 4 minutes (until dry).
EXAMPLE 1
To a round-bottom flask with a mechanical agitator were added 200.0 grams of
hyperbranched polyethyleneimine (sold under the name EPOMIN SP012 by
Summit Specialty Chemical, New Jersey) and 94.83 grams of stearic acid (sold
by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a Mõ of 1200.
The mixture was heated under nitrogen, with agitation, at a temperature of
about
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150 C for about 3 hours. At the end of the 3 hours, an aliquot was removed
and
analyzed using FT-IR, which indicated that no acid remained and that the
reaction was complete. The resulting product was a waxy solid.
The h-PEI derivative was dispersed into hot water via high speed and high
shear
agitation. To solubilize the h-PEI derivative, acetic acid was added to the
dispersions to achieve a pH level of about 5. The h-PEI derivative comprised
about 3.0% by weight of the dispersion. Also added to the dispersion was about
2.0% by weight of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOBO DAN).
The 100% polyester knit fabric used in Comparative Example A was dipped into
the dispersion and padded at a pressure of about 40 p.s.i. to remove excess.
The fabric was then dried at a temperature of about 370 F for about 3 minutes
(until dry).
EXAMPLE 2
To a round-bottom flask with a mechanical agitator were added 100.0 grams of
hyperbranched polyethyleneimine (sold under the name EPOMINO SP200 by
Summit Specialty Chemical, New Jersey) and 170.7 grams of isostearic acid
(sold under the name PRISORINE by Uniqema, Delaware). The
hyperbranched polyethyleneimine had a Mõ of about 10,000. The mixture was
heated under nitrogen, with agitation, at a temperature of about 150 C for
about
3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using
FT-IR, which indicated that no acid remained and that the reaction was
complete. The resulting product was a viscous liquid.
The h-PEI derivative was dispersed into hot water via high speed and high
shear
agitation. To solubilize the h-PEI derivative, acetic acid was added to the
dispersions to achieve a pH level of about 5. The h-PEI derivative comprised
about 3.0% by weight of the dispersion. Also added to the dispersion was about
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2.0% by weight of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOBO DAN).
The 100% polyester knit fabric used in Comparative Example A was dipped into
the dispersion and padded at a pressure of about 40 p.s.i. to remove excess.
The fabric was then dried at a temperature of about 370 F for about 3 minutes
(until dry).
EXAMPLE 3
To a round-bottom flask with a mechanical agitator were added 100.0 grams of
hyperbranched polyethyleneimine (sold under the name LUPASOLO WF by
BASF, New Jersey) and 284.5 grams of stearic acid (sold by Aldrich,
Wisconsin).
The hyperbranched polyethyleneimine had a Mõ of about 10,000. The mixture
was heated under nitrogen, with agitation, at a temperature of about 150 C
for
about 3 hours. At the end of the 3 hours, an aliquot was removed and analyzed
using FT-IR, which indicated that no acid remained and that the reaction was
complete. The resulting product was a waxy solid.
To a stainless steel reactor with agitator and temperature controller were
added
300.0 grams of the h-PEI derivative formed above. The h-PEI derivative was
heated to about 250 F, after which 42.0 grams of ethylene oxide slowly were
added until all of the ethylene oxide was reacted, as measured by the hydroxyl
number. The resulting capped h-PEI derivative was a paste at room
temperature.
The capped h-PEI derivative was dispersed into hot water via high speed and
high shear agitation. To solubilize the h-PEI derivative, acetic acid was
added to
the dispersions to achieve a pH level of about 5. The h-PEI derivative
comprised
about 5.7% by weight of the dispersion. Also added to the dispersion was about
2.0% by weight of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOBO DAN).
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The 100% polyester knit fabric used in Comparative Example A was dipped into
the dispersion and padded at a pressure of about 40 p.s.i. to remove excess.
The fabric was then dried at a temperature of about 370 F for about 3 minutes
(until dry).
EXAMPLE 4
To a round-bottom flask with a mechanical agitator were added 200.0 grams of
hyperbranched polyethyleneimine (sold under the name EPOMIN SP012 by
Summit Specialty Chemical, New Jersey) and 94.83 grams of stearic acid (sold
by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a Mõ of 1200.
The mixture was heated under nitrogen, with agitation, at a temperature of
about
150 C for about 3 hours. At the end of the 3 hours, an aliquot was removed
and
analyzed using FT-IR, which indicated that no acid remained and that the
reaction was complete. The resulting product was a waxy solid.
The h-PEI derivative was dispersed into hot water via high speed and high
shear
agitation. To solubilize the h-PEI derivative, acetic acid was added to the
dispersions to achieve a pH level of about 5. The h-PEI derivative comprised
about 3.0% by weight of the dispersion. Also added to the dispersion was about
2.0% by weight of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOB DAN). This is the
same treatment chemistry that was used in Example 1.
The nylon/cotton woven fabric used in Comparative Examples B-D was dipped
into the dispersion and padded at a pressure of about 40 p.s.i. to remove
excess. The fabric was then dried at a temperature of about 310 F for about
10
minutes (until dry).
EXAMPLE 5
To a round-bottom flask with a mechanical agitator were added 100.0 grams of
hyperbranched polyethyleneimine (sold under the name EPOMIN SP200 by
Summit Specialty Chemical, New Jersey) and 24.61 grams of stearic acid (sold
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by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a Mõ of
10,000. The mixture was heated under nitrogen, with agitation, at a
temperature
of about 150 C for about 3 hours. At the end of the 3 hours, an aliquot was
removed and analyzed using FT-IR, which indicated that no acid remained and
that the reaction was complete. The resulting product was a viscous liquid.
The h-PEI derivative was dispersed into hot water via high speed and high
shear
agitation. To solubilize the h-PEI derivative, acetic acid was added to the
dispersions to achieve a pH level of about 5. The h-PEI derivative comprised
about 3.0% by weight of the dispersion. Also added to the dispersion was about
2.0% by weight of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOBO DAN).
The nylon/cotton woven fabric used in Comparative Examples B-D was dipped
into the dispersion and padded at a pressure of about 40 p.s.i. to remove
excess. The fabric was then dried at a temperature of about 310 F for about
10
minutes (until dry).
EXAMPLE 6
To a round-bottom flask with a mechanical agitator were added 100.0 grams of
hyperbranched polyethyleneimine (sold under the name LUPASOLO WF by
BASF, New Jersey) and 14.23 grams of stearic acid (sold by Aldrich,
Wisconsin).
The hyperbranched polyethyleneimine had a Mõ of 10,000. The mixture was
heated under nitrogen, with agitation, at a temperature of about 150 C for
about
3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using
FT-IR, which indicated that no acid remained and that the reaction was
complete. The resulting product was a viscous liquid.
The h-PEI derivative was dispersed into hot water via high speed and high
shear
agitation. To solubilize the h-PEI derivative, acetic acid was added to the
dispersions to achieve a pH level of about 5. The h-PEI derivative comprised
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about 2.3% by weight of the dispersion. No cross-linking agent was included
with this formulation.
The nylon/cotton woven fabric used in Comparative Example E was dipped into
the dispersion and padded at a pressure of about 40 p.s.i. to remove excess.
The fabric was then dried at a temperature of about 330 F for about 4 minutes
(until dry).
EXAMPLE 7
To a round-bottom flask with a mechanical agitator were added 100.0 grams of
hyperbranched polyethyleneimine (sold under the name LUPASOLO WF by
BASF, New Jersey) and 14.23 grams of stearic acid (sold by Aldrich,
Wisconsin).
The hyperbranched polyethyleneimine had a Mõ of 10,000. The mixture was
heated under nitrogen, with agitation, at a temperature of about 150 C for
about
3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using
FT-IR, which indicated that no acid remained and that the reaction was
complete. The resulting product was a viscous liquid.
The h-PEI derivative was dispersed into hot water via high speed and high
shear
agitation. To solubilize the h-PEI derivative, acetic acid was added to the
dispersions to achieve a pH level of about 5. The h-PEI derivative comprised
about 2.3% by weight of the dispersion. Also added to the dispersion was about
1.5% by weight of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOB DAN).
The nylon/cotton woven fabric used in Comparative Example E was dipped into
the dispersion and padded at a pressure of about 40 p.s.i. to remove excess.
The fabric was then dried at a temperature of about 330 F for about 4 minutes
(until dry).
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EXAMPLE 8
To a round-bottom flask with a mechanical agitator were added 100.0 grams of
hyperbranched polyethyleneimine (sold under the name LUPASOL WF by
BASF, New Jersey) and 14.23 grams of stearic acid (sold by Aldrich,
Wisconsin).
The hyperbranched polyethyleneimine had a Mõ of 10,000. The mixture was
heated under nitrogen, with agitation, at a temperature of about 150 C for
about
3 hours. At the end of the 3 hours, an aliquot was removed and analyzed using
FT-IR, which indicated that no acid remained and that the reaction was
complete. The resulting product was a viscous liquid.
The h-PEI derivative was dispersed into hot water via high speed and high
shear
agitation. To solubilize the h-PEI derivative, acetic acid was added to the
dispersions to achieve a pH level of about 5. The h-PEI derivative comprised
about 2.3% by weight of the dispersion. Also added to the dispersion was about
1.5% by weight of a melamine-based cross-linking agent (available from Cytec
Industries under the tradename CYMEL 385).
The nylon/cotton woven fabric used in Comparative Example E was dipped into
the dispersion and padded at a pressure of about 40 p.s.i. to remove excess.
The fabric was then dried at a temperature of about 330 F for about 4 minutes
(until dry).
Odor Abatement Testing
A fabric sample (typically a 2-inch by 2-inch square) was positioned inside a
glass vial having an internal volume of about 20 mL and having a silicone cap.
1
microliter of an odor molecule mixture was injected into the vial. The vial
was
held at a temperature of about 40 C for about 1 hour. The chemical composition
of the void space at the top of the vial (that is, the "headspace") was
evaluated
using samples drawn from the vial and analyzed using a GC/MS. The numbers
shown in the TABLES below are relative within each individual table for a
given
volatile compound. The data are reduced representations of the areas obtained
directly from the GC peaks for a given compound. Higher numerical values
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reflect greater amounts of a particular volatile organic compound in the vapor
phase. Lower numerical values reflect fabric samples having greater adsorption
of odor-causing compounds.
For each of the Comparative Examples and the Example fabrics, head space
analysis was conducted to determine the presence of three different odor-
related
molecules (isobutyraldehyde, isovaleric acid, and limonene), which had been
added to the vials in approximately equal amounts by volume. Fabrics were
evaluated after initial preparation (that is, after 0 washes) and after
multiple
washes had occurred (for example, after 5 washes). The term "wash" refers to
laundering in a standard washing machine, using TIDEO powdered detergent,
according to AATCC Method 130 and subsequent drying in a hot air dryer.
TABLE 1: MEASURE OF VOLATILE COMPOUNDS
PRESENT IN HEADSPACE OF VIALS
CONTAINING COMPARATIVE EXAMPLE A
AND EXAMPLES 1-3 (POLYESTER KNIT FABRIC)
Sample ID 0 washes 5 washes 10 washes 20 washes
VOLATILE COMPOUND: ISOVALERIC ACID
Comp. Ex. A 75 648 1003 1283
Example 1 0 77 222 223
Example 2 0 82 212 146
Example 3 11 0 135 141
VOLATILE COMPOUND: ISOBUTYRALDEHYDE
Comp. Ex. A 50 80 134 183
Example 1 7 17 41 64
Example 2 12 38 61 58
Example 3 22 22 55 57
VOLATILE COMPOUND: LIMONENE
Comp. Ex. A 3839 4762 5923 7384
Example 1 3375 2252 3885 4551
Example 2 2819 2544 4020 4407
Example 3 2657 2238 3874 4281
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As shown from the test data above, the fabrics of Examples 1, 2, and 3
adsorbed
more volatile compounds from the headspace of their respective vials than did
Comparative Example A. The treatment chemistry was particularly effective at
adsorbing isovaleric acid, which is a primary component of human sweat odors.
The treatment chemistry also worked exceptionally well at adsorbing
isobutyraldehyde, and performed better than the Comparative Example at
adsorbing limonene. It should also be noted that the superior performance of
Examples 1-3 was especially evident after the samples had been subjected to
multiple launderings.
TABLE 2: MEASURE OF VOLATILE COMPOUNDS
PRESENT IN HEADSPACE OF VIALS
CONTAINING COMPARATIVE EXAMPLES B, C, AND D
AND EXAMPLES 4 AND 5 (NYLON/COTTON WOVEN FABRIC) --F Sample ID E 0 washes 5
washes 10 washes
VOLATILE COMPOUND: ISOVALERIC ACID
Comp. Ex. B 204 936 809
Comp. Ex. C 219 843 829
Comp. Ex. D 393 606 868
Example 4 0 86 165
Example 5 0 58 180
VOLATILE COMPOUND: ISOBUTYRALDEHYDE
Comp. Ex. B 337 286 319
Comp. Ex. C 339 287 305
Comp. Ex. D 368 316 316
Example 4 192 296 326
Example 5 191 243 313
VOLATILE COMPOUND: LIMONENE
Comp. Ex. B 7267 8385 8720
Comp. Ex. C 7306 7922 8115
Comp. Ex. D 6012 6538 6798
Example 4 6949 6384 6481
Example 5 7269 6098 6680
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As shown from the test data above, the fabrics of Examples 4 and 5 performed
better than, or equivalent to, Comparative Examples B, C, and D at adsorbing
volatile compounds from the headspace of their respective vials. The treatment
chemistry was particularly effective at adsorbing isovaleric acid. The
treatment
chemistry also worked well at adsorbing isobutyraldehyde and limonene,
although the performance was not as dramatic as with the polyester fabric
samples discussed above. Again, the decrease in odor adsorption with multiple
washes was less pronounced with Examples 4 and 5, as compared to
Comparative Examples B-D.
TABLE 3: MEASURE OF VOLATILE COMPOUNDS
PRESENT IN HEADSPACE OF VIALS
CONTAINING COMPARATIVE EXAMPLE E
AND EXAMPLES 6, 7, AND 8 (NYLON/COTTON WOVEN FABRIC)
Sample ID 0 washes 5 washes
VOLATILE COMPOUND: ISOVALERIC ACID
Comp. Ex. E 1803 1390
Example 6 5 76
Example 7 0 2
Example 8 0 0
VOLATILE COMPOUND: ISOBUTYRALDEHYDE
Comp. Ex. E 250 239
Example 6 41 158
Example 7 38 82
Example 8 42 102
VOLATILE COMPOUND: LIMONENE
Comp. Ex. E 9133 8625
Example 6 9142 7786
Example 7 8905 7675
Example 8 8849 7606
As shown from the test data above, the fabrics of Examples 6, 7, and 8
adsorbed
more volatile compounds from the headspace of their respective vials than did
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Comparative Example E. The treatment chemistry was particularly effective at
adsorbing isovaleric acid, and also worked exceptionally well at adsorbing
isobutyraldehyde. Further, the treatment chemistry performed better than
Comparative Example E, after both had been washed 5 times, at adsorbing
limonene. It should also be noted that the superior performance of Examples 7
and 8 was especially evident after the samples had been subjected to multiple
launderings.
The results shown above indicate that the present chemical treatment provides
odor abatement and that the chemical treatment is durable to laundering, both
of
which represent a useful advance over the_ prior art.
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