U.S. patent application number 11/651711 was filed with the patent office on 2008-07-10 for textiles treated with hyperbranched polyethyleneimine derivatives for odor control properties.
Invention is credited to Marie S. Chan, Xinggao Fang, Michael Hong, Michael Brett Meredith, Piyush Shukla.
Application Number | 20080164439 11/651711 |
Document ID | / |
Family ID | 39345502 |
Filed Date | 2008-07-10 |
United States Patent
Application |
20080164439 |
Kind Code |
A1 |
Fang; Xinggao ; et
al. |
July 10, 2008 |
Textiles treated with hyperbranched polyethyleneimine derivatives
for odor control properties
Abstract
The present disclosure is directed to synthetic textiles treated
with h-PEI derivatives, such derivatives possessing the general
structure shown below: (R).sub.x-h-PEI-(A).sub.y where R is a
non-hyperbranched hydrocarbon group, said hydrocarbon group having
at least one linear portion, said linear portion having between 5
and 30 carbon atoms; where x is a number from 1 to 10,000; where
h-PEI is a hyperbranched polyethyleneimine; where A is an organic
compound having from 1 to 4 carbon atoms; where y is a number from
0 to 500; and wherein R is present in an amount of between about
0.1% and about 80% by weight of the h-PEI derivative. The chemical
treatment imparts durable odor control, softness, wrinkle
resistance, and moisture wicking to substrates treated
therewith.
Inventors: |
Fang; Xinggao; (Duncan,
SC) ; Shukla; Piyush; (Greer, SC) ; Hong;
Michael; (Greer, SC) ; Meredith; Michael Brett;
(Hendersonville, NC) ; Chan; Marie S.; (Forrest
City, NC) |
Correspondence
Address: |
Legal Department (M-495)
P.O. Box 1926
Spartanburg
SC
29304
US
|
Family ID: |
39345502 |
Appl. No.: |
11/651711 |
Filed: |
January 10, 2007 |
Current U.S.
Class: |
252/8.61 ;
427/372.2 |
Current CPC
Class: |
D06M 2200/12 20130101;
D06M 16/00 20130101; C08G 18/8061 20130101; D06M 15/53 20130101;
D06M 15/61 20130101; C08L 79/02 20130101; C08G 73/0206 20130101;
C08G 18/6423 20130101; D06M 2200/20 20130101 |
Class at
Publication: |
252/8.61 ;
427/372.2 |
International
Class: |
D06M 15/21 20060101
D06M015/21 |
Claims
1. A treated textile substrate, said treated textile fabric
comprises: (a) a synthetic-containing textile substrate; and (b) a
treatment applied to at least one side of said textile substrate,
said treatment comprising: (i) a hyperbranched polyethyleneimine
derivative of the formula: (R).sub.x-h-PEI-(A).sub.y where R is a
non-hyperbranched hydrocarbon group, said hydrocarbon group having
at least one linear portion, said linear portion having between 5
and 30 carbon atoms; where x is a number from 1 to 10,000; where
h-PEI is a hyperbranched polyethyleneimine; where A is an organic
compound having from 1 to 4 carbon atoms; where y is a number from
0 to 500; and wherein R is present in an amount of between about
0.1% and about 20% by weight of said hyperbranched
polyethyleneimine derivative; and (ii) a cross-linking agent.
2. The treated textile substrate of claim 1, wherein said substrate
is a fabric.
3. The treated textile substrate of claim 1, wherein said treatment
is applied to said substrate at an add-on level of between about
0.1% to about 10%, based on the weight of said substrate.
4. The treated textile substrate of claim 3, wherein said treatment
is applied to said substrate at an add-on level of between about
0.2% to about 5%, based on the weight of said substrate.
5. The treated textile substrate of claim 1, wherein said h-PEI has
a number average molecular weight (M.sub.n) in the range of about
300 to about 2 million.
6. The treated textile substrate of claim 5, wherein said h-PEI has
a number average molecular weight (M.sub.n) in range of about 1,000
to about 75,000.
7. The treated textile substrate of claim 1, wherein said linear
portion of said R group has between about 10 and about 24 carbon
atoms.
8. The treated textile substrate of claim 1, wherein said h-PEI and
said R group are present, in a weight ratio, of from about 100:1 to
about 10:1.
9. The treated textile substrate of claim 1, wherein said A group
is at least one compound selected from the group consisting of
ethylene oxide, propylene oxide, butylene oxide, methyl, acetate,
vinyl sulfonate, trifluoroacetate, and trialkyl silyl.
10. The treated textile substrate of claim 9, wherein said A group
is ethylene oxide or propylene oxide.
11. The treated textile substrate of claim 1, wherein said R group
has a C.sub.17H.sub.35 structure, resulting in a stearic amide
linkage between said R group and said h-PEI.
12. The treated textile substrate of claim 1, wherein said
cross-linking agent is selected from the group consisting of
isocyanate cross-linking agents, protected isocyanate cross-linking
agents, and melamine formaldehyde cross-linking agents.
13. A process of treating a textile substrate, said process
comprising: (a) providing a synthetic-containing textile substrate;
(b) providing a dispersion comprising a hyperbranched
polyethyleneimine derivative and a cross-linking agent, said
hyperbranched polyethyleneimine derivative being of the formula:
(R).sub.x-h-PEI-(A).sub.y where R is a non-hyperbranched
hydrocarbon group, said hydrocarbon group having at least one
linear portion, said linear portion having between 5 and 30 carbon
atoms; where x is a number from 1 to 10,000; where h-PEI is a
hyperbranched polyethyleneimine; where A is an organic compound
having between 1 to 4; where y is a number from 0 to 500; and
wherein R is present in an amount of between about 0.1% and about
20% by weight of said hyperbranched polyethyleneimine derivative,
said dispersion containing said hyperbranched polyethylene
derivative being produced by: (i) providing said hyperbranched
polyethyleneimine derivative, a solubilizing agent, and water, said
water having a temperature at least equal to the melting point of
said hyperbranched polyethyleneimine derivative; and (ii)
subjecting said hyperbranched polyethyleneimine derivative, said
solubilizing agent, and said water to high speed and high shear
agitation; (c) applying said dispersion to said textile substrate;
and (d) drying said textile substrate.
14. The process of claim 13, wherein said textile substrate is a
fabric.
15. The process of claim 13, wherein said solubilizing agent is
acetic acid.
16. The process of claim 13, wherein heat is applied during step
(i) or step (ii) to facilitate formation of said dispersion.
17. A treated textile substrate, said treated textile fabric
comprises: (a) a synthetic-containing textile substrate; and (b) a
treatment applied to at least one side of said textile substrate,
said treatment comprising: a hyperbranched polyethyleneimine
derivative of the formula: (R).sub.x-h-PEI-(A).sub.y where R is a
non-hyperbranched hydrocarbon group, said hydrocarbon group having
at least one linear portion, said linear portion having between 5
and 30 carbon atoms; where x is a number from 1 to 10,000; where A
is an organic compound having from 1 to 4 carbon atoms; where y is
a number from 0 to 500; where h-PEI is a hyperbranched
polyethyleneimine; and wherein R is present in an amount of between
about 20% and about 80% by weight of said hyperbranched
polyethyleneimine derivative.
18. The product of claim 17, wherein said substrate is a
fabric.
19. A process of treating a textile substrate, said process
comprising: (a) providing a synthetic-containing textile substrate;
(b) providing a dispersion comprising a hyperbranched
polyethyleneimine derivative and a cross-linking agent, said
hyperbranched polyethyleneimine derivative being of the formula:
(R).sub.x-h-PEI-(A).sub.y where R is a non-hyperbranched
hydrocarbon group, said hydrocarbon group having at least one
linear portion, said linear portion having between 5 and 30 carbon
atoms; where x is a number from 1 to 10,000; where A is an organic
compound having from 1 to 4 carbon atoms; where y is a number from
0 to 500; where h-PEI is a hyperbranched polyethyleneimine; and
wherein R is present in an amount of between about 20% and about
80% by weight of said hyperbranched polyethyleneimine derivative,
said dispersion containing said hyperbranched polyethylene
derivative being produced by: (i) providing said hyperbranched
polyethyleneimine derivative, a solubilizing agent, and water, said
water having a temperature at least equal to the melting point of
said hyperbranched polyethyleneimine derivative; and (ii)
subjecting said hyperbranched polyethyleneimine derivative, said
solubilizing agent, and said water to high speed and high shear
agitation; (c) applying said dispersion to said textile substrate;
and (d) drying said textile substrate.
20. The process of claim 19, wherein said substrate is a
fabric.
21. The process of claim 19, wherein heat is applied during step
(i) or step (ii) to facilitate formation of said dispersion.
Description
TECHNICAL FIELD
[0001] 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.
[0002] 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.
[0003] 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.
[0004] 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.
BACKGROUND
[0005] 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.
[0006] 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.
[0007] 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).
[0008] 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.
[0009] 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.
[0010] 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
[0011] 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.
[0012] 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 or more additional organic "cap"
compounds attached to the hyperbranched polyethyleneimine core.
[0013] 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.
[0014] 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.
[0015] 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.
[0016] 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 embodiment,
the target fabric is placed into the chemical treatment (e.g, by
dipping), then padded and dried in a single continuous process.
[0017] 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
[0018] 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.RTM. and KEVLAR.RTM.) 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.
[0019] 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 average molecular weight (M.sub.n) of the h-PEI, which
reflects the number of branches available for attachment.
[0020] For the applications that are contemplated herein,
hyperbranched polyethyleneimines having a number average molecular
weight (M.sub.n) of between about 300 and about 2 million are
preferred, with M.sub.n of between about 1,000 and about 75,000
being more preferred.
[0021] 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.
[0022] 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.
[0023] 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 1:5, depending on the M.sub.n of the h-PEI. Most preferably,
weight ratios of h-PEI to hydrophobic group from about 1:1 to about
1:4 are used.
[0024] The present h-PEI derivatives possess the structure shown
below:
(R).sub.x-h-PEI-(A).sub.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 M.sub.n 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.
[0025] 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.
[0026] 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 NH.sub.2)
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.
[0027] 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.degree. 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.
[0028] One potentially preferred "R" group has a C.sub.17H.sub.35
structure, which in the above structure forms a stearic amide. When
using this R group and an h-PEI having an M.sub.n 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 M.sub.n 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 M.sub.n 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.
[0029] 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.degree. 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.
[0030] 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 weight of the h-PEI derivative, and more preferably,
from about 30% to about 75% of the weight of the h-PEI
derivative.
[0031] 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.RTM.-type agitators, homogenizers, roll
mill, ball mill, microfluidization, and the like.
[0032] 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.
[0033] 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.
[0034] The treated web is then removed from the solution and dried,
preferably at temperatures between room temperature and 400.degree.
F., and more preferably, at temperatures between about 100.degree.
F. to about 380.degree. 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.
[0035] 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.
[0036] 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.
[0037] 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 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.
[0038] Other finishing agents may also be used, such as wetting
agents, softeners, soil release agents, flame retardants, and the
like.
[0039] 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
[0040] 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.RTM. W7
HPTL) and 2.0% (by weight) of a blocked isocyanate cross-linking
agent (available from Clariant Corporation under the tradename
ARKOPHOB.RTM. 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.degree. F. for about 3 minutes (until dry).
COMPARATIVE EXAMPLE B
[0041] 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.degree. F. for about 10 minutes (until dry).
COMPARATIVE EXAMPLE C
[0042] 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.RTM. W7 HPTL) and 2.0% (by weight) of a
blocked isocyanate cross-linking agent (available from Clariant
Corporation under the tradename ARKOPHOB.RTM. 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.degree. F.
for about 10 minutes (until dry).
COMPARATIVE EXAMPLE D
[0043] 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.RTM. JVA) and 2.0% (by
weight) of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOB.RTM. 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.degree. F.
for about 10 minutes (until dry).
COMPARATIVE EXAMPLE E
[0044] 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 CAVATEX.RTM. W7 HPTL) and 1.0% (by
weight) of a blocked isocyanate cross-linking agent (available from
Clariant Corporation under the tradename ARKOPHOB.RTM. DAN) and
then padded at a pressure of about 40 p.s.i. to remove excess. The
fabric was then dried at about 330.degree. F. for about 4 minutes
(until dry).
EXAMPLE 1
[0045] To a round-bottom flask with a mechanical agitator were
added 200.0 grams of hyperbranched polyethyleneimine (sold under
the name EPOMIN.RTM. SP012 by Summit Specialty Chemical, New
Jersey) and 94.83 grams of stearic acid (sold by Aldrich, Wis.).
The hyperbranched polyethyleneimine had a M.sub.n of 1200. The
mixture was heated under nitrogen, with agitation, at a temperature
of about 150.degree. 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.
[0046] 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.RTM. DAN).
[0047] 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.degree. F. for about 3 minutes (until dry).
EXAMPLE 2
[0048] To a round-bottom flask with a mechanical agitator were
added 100.0 grams of hyperbranched polyethyleneimine (sold under
the name EPOMIN.RTM. SP200 by Summit Specialty Chemical, New
Jersey) and 170.7 grams of isostearic acid (sold under the name
PRISORINE.RTM. by Uniqema, Del.). The hyperbranched
polyethyleneimine had a M.sub.n of about 10,000. The mixture was
heated under nitrogen, with agitation, at a temperature of about
150.degree. 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.
[0049] 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.RTM. DAN).
[0050] 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.degree. F. for about 3 minutes (until dry).
EXAMPLE 3
[0051] To a round-bottom flask with a mechanical agitator were
added 100.0 grams of hyperbranched polyethyleneimine (sold under
the name LUPASOL.RTM. WF by BASF, New Jersey) and 284.5 grams of
stearic acid (sold by Aldrich, Wis.). The hyperbranched
polyethyleneimine had a M.sub.n of about 10,000. The mixture was
heated under nitrogen, with agitation, at a temperature of about
150.degree. 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.
[0052] 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.
[0053] 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
ARKOPHOB.RTM. DAN).
[0054] 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.degree. F. for about 3 minutes (until dry).
EXAMPLE 4
[0055] To a round-bottom flask with a mechanical agitator were
added 200.0 grams of hyperbranched polyethyleneimine (sold under
the name EPOMIN.RTM. SP012 by Summit Specialty Chemical, New
Jersey) and 94.83 grams of stearic acid (sold by Aldrich, Wis.).
The hyperbranched polyethyleneimine had a M.sub.n of 1200. The
mixture was heated under nitrogen, with agitation, at a temperature
of about 150.degree. 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.
[0056] 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.RTM. DAN). This
is the same treatment chemistry that was used in Example 1.
[0057] 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.degree. F. for about 10 minutes (until
dry).
EXAMPLE 5
[0058] To a round-bottom flask with a mechanical agitator were
added 100.0 grams of hyperbranched polyethyleneimine (sold under
the name EPOMIN.RTM. SP200 by Summit Specialty Chemical, New
Jersey) and 24.61 grams of stearic acid (sold by Aldrich, Wis.).
The hyperbranched polyethyleneimine had a M.sub.n of 10,000. The
mixture was heated under nitrogen, with agitation, at a temperature
of about 150.degree. 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.
[0059] 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.RTM. DAN).
[0060] 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.degree. F. for about 10 minutes (until
dry).
EXAMPLE 6
[0061] To a round-bottom flask with a mechanical agitator were
added 100.0 grams of hyperbranched polyethyleneimine (sold under
the name LUPASOL.RTM. WF by BASF, New Jersey) and 14.23 grams of
stearic acid (sold by Aldrich, Wis.). The hyperbranched
polyethyleneimine had a M.sub.n of 10,000. The mixture was heated
under nitrogen, with agitation, at a temperature of about
150.degree. 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.
[0062] 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. No cross-linking agent was included with this
formulation.
[0063] 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.degree. F. for about 4 minutes (until dry).
EXAMPLE 7
[0064] To a round-bottom flask with a mechanical agitator were
added 100.0 grams of hyperbranched polyethyleneimine (sold under
the name LUPASOL.RTM. WF by BASF, New Jersey) and 14.23 grams of
stearic acid (sold by Aldrich, Wis.). The hyperbranched
polyethyleneimine had a M.sub.n of 10,000. The mixture was heated
under nitrogen, with agitation, at a temperature of about
150.degree. 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.
[0065] 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.RTM. DAN).
[0066] 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.degree. F. for about 4 minutes (until dry).
EXAMPLE 8
[0067] To a round-bottom flask with a mechanical agitator were
added 100.0 grams of hyperbranched polyethyleneimine (sold under
the name LUPASOL.RTM. WF by BASF, New Jersey) and 14.23 grams of
stearic acid (sold by Aldrich, Wis.). The hyperbranched
polyethyleneimine had a M.sub.n of 10,000. The mixture was heated
under nitrogen, with agitation, at a temperature of about
150.degree. 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.
[0068] 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.RTM. 385).
[0069] 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.degree. F. for about 4 minutes (until dry).
Odor Abatement Testing
[0070] 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 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.
[0071] 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 TIDE.RTM.) powdered detergent, according to
AATCC Method 130 and subsequent drying in a hot air dryer.
TABLE-US-00001 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
[0072] 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-US-00002 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) Sample ID 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
[0073] 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-US-00003 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
[0074] 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 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.
[0075] 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.
* * * * *