Note: Descriptions are shown in the official language in which they were submitted.
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RING DYED POLYMER TREATED MATERIALS
Background
[0001] Color has been applied to textiles over the ages. Natural
colorants derived
from plants and earthen surroundings were used before a dyestuff industry came
into being.
Issues with dye fixation, durability, light fastness, colorfastness, and depth
of color all
remained challenges. As the chemistry of dyes became known and a synthetic
approach to
engineering dyes to adhere to specific fibers abounded, dyes were created with
different
mechanisms to become attached to various fiber classes. For cellulosic
materials, vat dyes
were rendered soluble with reducing materials, and subsequently fixed through
oxidization
once the dye had penetrated the fiber. Also used were metalized mordants that
when applied
to a natural fiber could be coupled with a water soluble colorant to
precipitate the dye once
in the fiber. To capitalize on the solubility of dye components for coloring
textiles, naphthol
dyes were applied and upon coupling with a companion base, an insoluble
colorant resulted ¨
trapped within the fiber matrix.
[0002] As film forming materials were introduced into the dyeing process,
new
methods to apply colorants to textiles through padding and printing methods
became
possible. In this dyeing application, the polymeric binder and colorant were
generally mixed,
applied together, and the pigment color generally left on the surface.
Attempts to incorporate
other colorants in this mixture generally resulted in poor colorfastness or
light fastness
performance issues.
[0003] There have been many attempts to create "ring dyed" yarns. The
most
common and prevalent is that of the dyeing of indigo to produce denim. By
multiple steps of
dipping and oxidizing the dye onto yarn, the dye penetrates only partially
into the yarn
bundle. The resultant "ring dyeing" creates light and dark highlights on
abrasion points once
a garment is sewn and processed using chemical and physical abrasive means
before and
during a laundering process.
[0004] Ring dyeing is also generally achieved with the application of
pigment dyes
mixed with binders. This approach has resulted in fabric with stiff handle and
marginal rub-
fastness performance; however, with advances in acrylic polymer chemistry
featuring co and
ter polymer blends with lower Tg values, softer and more durable polymers have
been
created. Even with advances to improve performance, color choice and depth of
shade versus
rub fastness performance remain challenges. Efforts to improve rub fastness
performance
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through new polyvinyl alcohol emulsion systems have met with some improvement.
(See
Schoots et al., U.S. Patent Application Publication No. 2011/0009021 Al).
Summary
[0005] The following presents a simplified summary of one or more
embodiments of
the invention in order to provide a basic understanding of such embodiments.
This summary
is not an extensive overview of all contemplated embodiments, and is intended
to neither
identify key or critical elements of all embodiments, nor delineate the scope
of any or all
embodiments. Its sole purpose is to present some concepts of one or more
embodiments in a
simplified form as a prelude to the more detailed description that is
presented later.
[0006] In a first aspect, a dye binding composition for a ring dyed
material is
provided, the composition comprising a urethane based polymer having a solids
percentage in
the composition of between 0.5% and 50% by weight. In some embodiments, the
solids
percentage in the composition is between 2.0% and 12.0%. In some embodiments,
the
composition further includes a cationic material. In still further
embodiments, the cationic
material is selected from the group consisting of guanidine and urethane. In
yet still further
embodiments, the composition further includes a UV inhibitor. In some
embodiments, the
urethane based polymer is a polyurethane dispersion.
[0007] In a second aspect, a ring dyed yarn including at least one fiber;
and a dye
binding composition for a ring dyed material is provided, the composition
comprising a
urethane based polymer having a solids percentage in the composition of
between 0.5% and
50% by weight. In some embodiments, the yarn includes at least one dye
configured to
selectively dye the dye binding composition positioned on at least a portion
of the surface of
the fiber. In further embodiments, at least some of the dye binding
composition is positioned
on at least a portion of the surface of the fibers. In a still further
embodiment, the fiber is
selected from the group consisting of cotton, wool, silk, hemp, flax,
polyester, rayon, acetate,
nylons, spandex, olefins, polyethylene, polyethylene, and polypropylene.
[0008] In a third aspect, a fabric including fibers; a dye binding
composition for a
ring dyed material, the composition comprising a urethane based polymer having
a solids
percentage in the composition of between 0.5% and 50% by weight, wherein at
least some of
the dye binding composition is positioned on at least a portion of the surface
of the fibers;
and at least one dye configured to selectively color the dye binding
composition positioned
on at least a portion of the surface of the fibers is provided. In some
embodiments, the dye
binding composition further includes a cationic material selected from the
group consisting of
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guanidine and urethane. In still further embodiments, the at least one dye
does not directly
dye the fibers. In some embodiments, the fabric comprises denim. In some
embodiments,
the fibers include at least one of cotton fibers and synthetic fibers.
[0009] In a fourth aspect, a garment including fabric comprising fibers;
a dye binding
composition for a ring dyed material, the composition comprising a urethane
based polymer
having a solids percentage in the composition of between 0.5% and 50% by
weight, wherein
at least some of the dye binding composition is positioned on at least a
portion of the surface
of the fibers; and at least one dye configured to selectively dye the dye
binding composition
positioned on at least a portion of the surface of the fibers is provided. In
some
embodiments, the garment includes a first surface area comprising the dye
binding
composition that has been dyed with the at least one dye and a second surface
area that is free
of the dye binding composition.
[0010] In a fifth aspect, a method of producing ring dyed or surface dyed
fiber, yarn,
fabric, or garment is provided, the method including applying a dye binding
composition for
a ring dyed material to at least one of the fiber, yarn, fabric, or garment,
the composition
comprising a urethane based polymer having a solids percentage in the
composition of
between 0.5% and 50% by weight; heating the fiber, yarn, fabric, or garment to
cause the dye
binding composition to mobilize to a surface of the fiber, yarn, fabric, or
garment; and
applying at least one selective dye to the at least one of the fiber, yarn,
fabric, or garment,
wherein the selective dye is selective for the dye binding composition.
[0011] In some embodiments, the dye binding composition and the selective
dye are
applied simultaneously. In some embodiments, the dye binding composition and
the
selective dye are applied sequentially. In further embodiments, the method
further includes
abrading at least a portion of the surface of the garment to remove at least
some of the dye
binding composition that has been dyed with the at least one dye such that the
garment has
first areas comprising fibers that comprise the dye binding composition that
has been dyed
with the at least one dye and second areas comprising fibers that do not
include the dye
binding composition. In some embodiments, the abrading is performed based on
at least one
of: sanding; application of diatomaceous earth; and application of pumice
stones to the
garment. In still further embodiments, the heating the dye binding composition
is performed
using at least one of a curing oven, steam cans, and hot flue. In still
further embodiments, the
selective dye is applied using at least one of thermosol dyeing on a
continuous dye range or
tenter frame, pad steaming on a continuous pad/steam range or flash ageing
machine, jet
dyeing, jigger dyeing, beam dyeing, pad/dry/thermosol dyeing, and printing.
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[0012] Other aspects and features, as recited by the claims, will become
apparent to
those skilled in the art upon review of the following non-limited detailed
description of the
invention in conjunction with the accompanying figures.
Brief Description of the Drawings
[0013] Having thus described embodiments of the invention in general
terms,
reference will now be made to the accompanying drawings, which are not
necessarily drawn
to scale, and wherein:
[0014] FIG. 1 is a diagram showing the impact of shade on chemical
application at
varying dye concentrations, in accordance with an embodiment of the
disclosure.
Detailed Description
[0015] Embodiments of the present invention will now be described more
fully with
reference to the accompanying examples and drawings, in which some, but not
all,
embodiments of the invention are shown. Indeed, the invention may be embodied
in many
different forms and should not be construed as limited to the embodiments set
forth herein;
rather, these embodiments are provided so that this disclosure may satisfy
applicable legal
requirements. Like numbers refer to like elements throughout.
[0016] Where possible, any terms expressed in the singular form herein
are meant to
also include the plural form and vice versa, unless explicitly stated
otherwise. Also, as used
herein, the term "a" and/or "an" shall mean "one or more," even though the
phrase "one or
more" is also used herein. It should also be understood that while some
embodiments
describe the methods or products as comprising one or more elements, the
methods or
elements may also consist of or consist essentially of the elements disclosed
herein.
[0017] As disclosed herein, a dye binding composition for preparing a
ring dyed yarn
and/or a surface dyed material is provided. In an embodiment, the surface dyed
material is
prepared with the ring dyed yarn. In some embodiments, the dye binding
composition
includes a polymer and/or additives that are engineered to either provide a
minimum or
maximum degree of migration to position the composition within or on a fiber
surface
depending on molecular weight and monomer selection. The polymer is generally
applied in
an aqueous media and can be formulated from a number of monomers in the
urethane,
guanidine, azetidinium, and vinyl halogen families to form polymer emulsions.
The solids
added on to the textile substrate can range from 0.5% to 50% by weight; but
generally 2.0%
to 12.0% percent is desired. Additionally, the polymer has good film forming
properties, is
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durable to laundering conditions, has the ability to incorporate materials
that can provide
targeted dyestuff attraction and durability, and/or is capable of fixing the
dye in its matrix.
[0018] In some embodiments, the dye binding composition comprises a
urethane
based polymer with a molecular weight ranging from 1,000 to 400,000 g/mole. In
an
embodiment, the urethane based polymer has a molecular weight ranging from
2,000 to
200,000 g/mole. The urethane based polymer is designed to attract and hold
selective dyes;
however, in some embodiments, additional materials can be added as discussed
below. The
urethane based polymer, in some embodiments, comprises a polyurethane
dispersion. The
term "polyurethane dispersion" as used herein describes stable mixtures of
polyurethane
polymers in water. Polyurethane polymers are generally characterized by their
monomer
content and most commonly involve the reaction of a diisocyanate with a polyol
and chain
extender. The polyurethane dispersion can be a stable aqueous mixture of any
known
polyurethane. Typically, the polyurethanes suitable for use in the aqueous
polyurethane
dispersions are the reaction products (a) an isocyanate compound having at
least two
isocyanate (--NCO) functionalities per molecule; and (b) a polyol having at
least two hydroxy
functionalities per molecule and a molecular weight ranging from 250 to 10,000
g/mole.
[0019] Exemplary polyol include hydroxy-containing or terminated
polyethers,
polyesters, polycarbonates, polycaprolactones, polythioethers,
polyetheresters, polyolefins,
and polydienes. Suitable polyether polyols for the preparation of polyether
polyurethanes
and their dispersions include the polymerization products of cyclic oxides
such as ethylene
oxide, propylene oxide, tetrahydrofuran, or mixtures thereof Polyether polyols
commonly
found include polyoxyethylene (PEO) polyols, polyoxypropylene (PPO) polyols,
polyoxytetramethylene (PTMO) polyols, and polyols derived from the mixture of
cyclic
oxides such as poly(oxyethylene-co-polypropylene) polyols. Typical molecular
weight of
polyether polyols can range from 250 to 10,000 g/mole.
[0020] Suitable polyester polyols for the preparation of polyester
polyurethanes and
their aqueous dispersions include hydroxy-terminated or containing reaction
products of
ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1-4,
butanediol, furan
dimethanol, polyether diols, or mixtures thereof, with dicarboxylic acids or
their ester-
forming derivatives. Modified polyether polyurethanes such as polyetherester
polyurethanes
and polyethercarbonate polyurethanes may also be suitable polyurethanes for
the preparation
of aqueous polyurethane dispersions. These modified polyether polyurethanes
can be derived
by incorporating additional polyester polyols or polycarbonate polyols into
polyether polyols
during the polyurethane manufacturing. The polyurethane dispersion as
component in the
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compositions of the dye binding composition is selected from polyether
polyurethanes,
polyester polyurethanes, polycarbonate polyurethanes, polyetherester
polyurethanes,
polyethercarbonate polyurethanes, polycaprolactone polyurethanes, hydrocarbon
polyurethanes, aliphatic polyurethanes, aromatic polyurethanes, and
combinations thereof.
[0021] Polyurethane dispersion as used herein encompasses both
conventional
emulsions of polyurethane polymers, for example where a preformed polyurethane
polymer
is emulsified into an aqueous medium with the addition of surfactants and
application of
shear, and also includes stable mixtures of self-dispersing polyurethane
polymers. These
polyurethane dispersions are generally free of external surfactants because
chemical moieties
having surfactant like characteristics have been incorporated into the
polyurethane polymer
and therefore are "self emulsifying" or "self dispersing." Representative
examples of internal
emulsifier moieties that can be incorporated into the polyurethane dispersions
useful in the
present invention include ionic groups such as sulfonates, carboxylates, and
quaternary
amines, as well as nonionic emulsifier groups such as polyethers.
[0022] In an embodiment, an isocyanate-terminated polyurethane prepolymer
is made
from isocyanates, polyols, optional chain extender, and at least one monomer
containing a
hydrophilic group to render the prepolymer water dispersible. The polyurethane
dispersion
can then be prepared by dispersing the isocyanate-terminated polyurethane
prepolymer in
water with other polyisocyanates. Further chain extension can be affected by
the addition of
chain extenders to the aqueous dispersion. Depending on the choice of the
hydrophilic group
used to render the polyurethane polymer water dispersible, an additional
reaction step may be
needed to convert the hydrophilic group to an ionic species, for example
converting a
carboxyl group to an ionic salt or an amine to an amine salt or cationic
quaternary group.
[0023] For dyeing with selective dyes, materials that can attract
targeted dyes within
the polymeric matrix are incorporated into the dye binding composition. In
some
embodiments, the dye binding composition comprises cellulose esters including
cellulose
acetate, cellulose propionate, cellulose butyrate, and combinations thereof.
In other
embodiments, the dye binding composition comprises the polymer and the
cellulose ester. In
further embodiments, the total solids of the dye binding composition is 50%,
where the
concentration of one or more of the cellulose esters is in the range of 1.0%
to 25% solids and
the concentration of the polymer is 25% to 49% solids. The one or more
cellulose esters, in
some embodiments, comprise finely ground powder having a particle size ranging
from 0.5
microns to 10 microns. In other embodiments, the finely ground powder of the
cellulose
esters have a particle size ranging from 1 micron to 3 microns. In further
embodiments, the
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cellulose ester is added to the dye binding composition in powder form. The
total solids of
the emulsion may vary between 10% and 60% in concentrated form, with the ratio
of the
polymer to the one or more cellulose esters remaining between 2% and 50% of
the total
solids percentage.
[0024] In some embodiments, the dye binding composition is applied to
fibers, yarns,
fabrics, and garments in concentrations ranging from 0.5% to 50% solids;
however, with
greater percent solids come greater expense and greater stiffness. In one
embodiment, the
percent solids range to be applied to the fibers, yarns, fabrics, or garments
is between 2.0 and
12.0%. In further embodiments, the percent solids range to be applied to the
fibers, yarns,
fabrics, or garments is between 3.0 and 10.0%. The dye binding composition,
including the
percentage of solids in the composition, is specifically engineered to produce
a dye binding
composition that causes the polymer and/or selective dye to migrate to the
surface for use in
producing ring dyed yarns and/or surface dyed fabrics.
[0025] Yarns and fabrics can be constructed from any of a host of textile
fiber,
particularly natural fibers including cotton, wool, silk, hemp, flax, or
synthetic fibers
including polyesters, rayon, acetate, acrylics, nylons (aromatic and
aliphatic), modacrylics,
spandex, olefins inclusive of super high molecular weight polyethylene,
polyethylene,
polypropylene, etc., or combinations of two or more of these fibers. In some
embodiments,
the yarn contains fiber comprised of 100% cotton. In other embodiments, the
yarns comprise
cotton fibers blended with non-cotton fibers. The blend of fibers, in some
embodiments, is at
least 50% cotton fibers.
[0026] In some embodiments, the dye binding composition further includes
a UV
inhibitor to improve light fastness performance, such as hindered amine light
stabilizers
(HALS). The light stabilizer can be added to the polymer mixture prior to
application or after
the polymer has cured either as a part of a dye mixture or alone. Both methods
have shown
effectiveness at improving lightfastness performance. Several low and high
molecular
materials are commercially available from companies including Cytec, Clariant,
Great Lakes,
and Ciba/Huntsman. An exemplary UV inhibitor includes a high molecular weight
material
that can be incorporated into the bath and that will eventually migrate to the
surface of the
film as the polymer film is formed upon drying. One Example is TINUVINO 622
from
CIBAO Chemical Company with a molecular weight of around 4000. These UV
inhibitors
can also be added to the final finishing bath to coat the surface of the
polymer before or after
the application of dye. UV absorbing materials are also available that can
serve a similar
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purpose through a different mechanism typically in the benzotriazole family
and are available
from Cytec.
[0027] In further embodiments, the dye binding composition comprises a
cationic
polymer that is incorporated into the urethane matrix. Such embodiments are
useful for
dyeing with acid dyes or acidified reactive dyes. The cationic polymer
comprises guanidine
and/or urethane. The guanidine and urethane can be combined to create a
polymeric film that
is cationic depending upon the percentage of the guanidine that has been
incorporated into the
matrix. In some embodiments, the dye binding composition comprises guanidine
and a
urethane based polymer. In further embodiments, the total percent solids of
the dye binding
composition is 50% solids, where the guanidine makes up 5% to 45% solids of
the total
solids percentage of the dye binding composition and the urethane based
polymer makes up
45% to 5% of the total solids percentage of the dye binding composition. In
one
embodiment, the urethane based polymer is present in the dye binding
composition at a
greater percentage than the cationic material. In a further embodiment, the
urethane based
polymer is present in the dye binding composition at a lesser percentage or at
an
approximately equal percentage (e.g., plus or minus 5%) of the cationic
material.
[0028] In the application process of the dye binding composition, process
conditions
and chemical concentrations dictate the resulting appearance and degree to
which penetrative
dyeing or ring dyeing occurs. In the case in which penetrative dyeing is
desired, drying of
the polymer is done slowly or anti-migrating agents are incorporated into the
mix prior to the
drying process. When fabrics with the same percent solids add on are compared,
fabrics that
are dried slowly result in a shade after dyeing that is lighter than the shade
after dyeing for
fabrics that are dried at a more rapid rate. It is believed that this result
is a direct result of the
polymer being on the surface of the substrate. However, the intent of this
technology is to
engineer dye binding compositions that cause a polymer and/or dye to migrate
to the surface
of a material, creating ring dyed yarns and/or surface dyed fabrics.
[0029] The mix to be applied to the textile substrate is generally
prepared by blending
the dye binding composition with water having a temperature range of 80 to
100
Fahrenheit. In an embodiment, the pH of the water/polymer mixture is not less
than 6.0 and
not greater than 8.0 after the addition of the polymer; however, pH levels
slightly outside this
range have not been shown to be detrimental. Anti-migrating agents and UV
inhibitors may
be added at this time if desired. The polymer percent solids concentration
range of the dye
binding composition is, in some embodiments, from 1% to 25% solids. In one
exemplary
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embodiment, the dye binding composition has a percent solids concentration
range of
between 2% and 12% solids depending on hand and depth of color considerations.
[0030] The dye binding composition is formulated based on the yarn,
fabric, or
garment wet pickup in order to provide the appropriate targeted percent solids
add on of
between 2.0% and 12%. For the application of this chemical mixture to cotton,
pad wet
pickups will generally vary from 45% to 220% depending on pad nip pressures,
post
vacuuming of fabric, bath viscosity, and/or absorbency of the padded material.
Percent wet
pickup is calculated as the [(fabric wet weight after padding)-(fabric dry
weight before
padding)]/(fabric dry weight before padding) * 100. For example, the wet
pickup of most
100% cotton fabrics ranges from 85 to 100%, so to achieve a solids add-on of
3%, a bath
concentration of 3% solids (6% of the dye binding material with 50% active
solids material)
with a wet pick-up of 100% would yield the appropriate solids addition. Lower
moisture add
on applications as low as 10% have been demonstrated using foaming techniques;
however,
the main body of the work has been done with more conventional chemical
application
techniques. Using foaming techniques, wet pickup levels generally are
controlled between 20
and 40% depending upon the amount of moisture needed on the fabric for
finishing and the
appearance desired.
[0031] Once the dye binding composition has been applied to the yarn or
fabric, the
evenness and rate of drying determines the amount of chemical that migrates to
the fabric
surface. The faster the fabric is dried, the greater the polymer migration to
the surface. This
impacts the degree of ring dyeing that will result from the application. For
more controlled,
slower drying, the fabric can be processed through pre-dryers prior to drying
and curing on a
tenter frame. For a penetrative dyeing in which minimal polymer migration is
desired, fabric
can be processed on a tenter frame such that the fabric is only partially
dried. This can be
accomplished by lowering the tenter zone temperatures and increasing the speed
of the fabric.
The moisture level of the fabric should be controlled to between 8 and 15%.
Final drying and
curing is achieved in subsequent processing.
[0032] For a ring-dye look, more rapid drying is used for the polymer of
the dye
binding composition to migrate to the yarn or fabric surface. This is achieved
by processing
the fabric or yarn at higher temperatures and curing the polymer on the
initial tenter pass.
This drying can also be achieved in a curing oven, steam cans, hot flue, or
other heat source
that promotes the movement of water and the polymer to the surface.
[0033] In the case of applying the chemical to yarn, yarns may be coated
and the
polymer of the dye binding composition dried such that the yarns are not
broken from being
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stuck together after drying. The dye binding composition can be applied to
scoured yarn,
scoured & bleached yarn, or yarn in its raw state. Each condition provides a
different
appearance with the raw yarn providing the greatest ring dyed characteristic.
Bath
concentrations are also different under each condition because of the
absorbency of the yarn
for the polymer/water mixture; however, targeted solids addition range from
2.0% to 12.0%
depending upon the size of the yarn being treated.
[0034] There are many ways in which the yarn can be coated. One method is
to
process the yarn through a pad with the dye binding composition comprising the
mixture of
polymer, water, and auxiliaries. The bath temperature can be adjusted to
between 65 and
190 F; however, the most consistent results occur when the bath temperature
is controlled to
between 80 and 100 F. Drying can be done using a forced air oven, pre-
dryers, a thermosol
oven, hot flue oven, microwave or steam cans, or a combination of any of the
above. Treated
yarns are collated on either a loom beam or a section beam for future
processing. A resulting
section beam comprised of treated yarns can be combined with many other beams,
sized with
an easily removed material such as starch or polyvinyl alcohol, or if
sufficient polymer has
been applied, not sized at all. By employing a combination of these
application techniques,
using the treated yarns in the warp direction, and subsequently weaving the
fabric with raw,
scoured, bleached, or dyed filling yarn, the resultant fabric can then be dyed
with dyes
targeted to dye the polymeric material of the dye binding composition. Dyes
are selected for
their propensity to not stain cotton ¨ both in the dyeing stage and in the
washing stage when
the polymeric material is being applied to cotton or cotton blends and a ring
dyed appearance
is desired. In a further embodiment of application of chemical to yarn,
chemical can be
applied to the yarn by passing it through a foaming unit allowing both
chemical and moisture
to be metered onto the fabric. This technique minimizes chemical waste and
allows specific
levels of the dye bonding polymer to be applied to the yarn.
[0035] Filling yarn selection will determine the processing steps that
follow. Most
denim fabrics directed to the men and boy's denim market contain no stretch
yarns, such as
spandex. For the women's market, stretch yarns are generally employed in the
filling
direction. The dyeing and finishing processes required to develop and maintain
the stretch
characteristics must be carefully controlled to prevent degradation of the
elastic effect of the
spandex or other stretch material.
[0036] Once the fabric has been woven, the fabric will appear as most
other undyed,
greige fabric. Dye can be applied either in fabric form or garment form
depending upon the
dye binding composition selected. Exemplary dyes include acid dyes and
selectively reactive
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dyes for the polymer containing guanidine or other cationic materials, and
disperse dyes for
any of the dye binding compositions. One advantage of dyeing in fabric form is
the ability to
see the color and shade of the fabric before going to the customer. In
addition, fabric panels
can be prepared and laundered to ensure that the shade of the fabric is
consistent before
constructing garments and laundering them to create denim appearing garments.
This
approach allows the flexibility to produce denim appearing fabric and garments
in multiple
colors, depth of color, and engineered color retention depending on the
polymer selected and
the penetration of the material during processing.
[0037] There are a number of ways in which this resulting denim fabric
can be dyed.
In one embodiment, the polymer of the dye binding composition is engineered to
accept
selective dyes. One dyeing method is to apply dyes in a pad, dry the fabric,
and heat the
fabric to between 390 and 425 F for a minimum of 30 seconds depending on the
selective
dye. In an embodiment, the dyes are designed to sublime (transform from a
solid state to a
gaseous state) between these temperatures. In the gaseous state, the dyes are
selectively
attracted to the polyurethane polymer and/or the cellulose acetate material
within the
polymeric matrix, and generally not to the cellulosic fibers of the fabric.
Subsequent washing
is generally effective at removing selective dye not fixed within the
polymeric matrix if the
dyes are properly chosen and the proper washing conditions are utilized. Care
must be used
with this approach if stretch fibers are incorporated within the fabric
because spandex can be
reset or degraded at these elevated temperatures.
[0038] The fabric is finished by the application of sewing lubricants and
water soluble
hand-builders if needed. These are generally applied in a pad or foamed onto
the fabric prior
to drying on a tenter frame. The final process involves preshrinking the
fabric and adding a
uniform skew in the direction of the twill line. This prevents twisted legs in
finished
garments, and ensures that the shrinkage of the fabric when wet processed does
not exceed
3%. Before the sanforization process, fabric shrinkage in the warp or
lengthwise direction for
high cotton blends ranges from 8% to 12%.
[0039] Another method of applying color to the treated fabric is to apply
the selective
dye in a pad and steam the fabric for a period of between 30 seconds and 3
minutes. The
polymer and cellulose acetate generally will dye under these conditions
depending upon the
dye selection and polymer selection. This steaming process may be used for
stretch fabrics
for which the substrate will be dyed in fabric rather than garment form.
[0040] For stretch fabrics, the finishing process may include a
heatsetting step to
stabilize the width of the fabric. The application of finishing chemicals
including a UV
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stabilizer can occur in this stage. Spandex or stretch polyesters in the
filling direction will
have a tendency of staining or becoming colored in this application; therefore
it is better to
have a core spun cotton spandex stretch yarn than one comprised of a composite
polyester
yarn such as LYCRA T-400 by INVISTATm or filling yarn comprised of poly-
butylene
terephthalate. The best results have been demonstrated on core spun products
consisting of
cotton with a spandex core.
[0041] One significant advantage to this process is that it bypasses the
need to dye the
yarn in rope form on a denim range, apply size, and then spend time, energy,
and chemical
resources to remove all of the size and some of the color to create a finished
garment. In
addition, the amount of selective dye needed to achieve saturated shades
ranges from 0.5 to
2.0% OWG instead of the higher 3 to 5 percent OWG indigo concentrations
desired for
denim.
[0042] By using the dye binding composition in the processes described
hereinabove,
garments can be laundered in cold water for lesser periods of time and with
fewer chemicals
depending on the desired appearance after laundering. The elimination of
amylase enzymes
to remove starch, cellulase enzyme to degrade the fabric surface, hypochlorite
bleach or
potassium permanganate to remove color, and the resulting byproducts from
these processes
have been shown to produce a positive environmental impact resulting from
reduced solids
generation and energy usage during the wet processing of garments.
Furthermore, the
elimination of these chemicals and processing at lower temperatures also
results in monetary
savings.
[0043] One additional option for the dye binding composition is to dye
the fabric after
garments are sewn using selective dyes in the wet processing step. For
example, garments
are placed in a laundering machine, water added to produce a 4:1 to 20:1
liquor to goods
ratio, the pH adjusted to 4.0 with acetic acid, 0.5% and 3% OWG (on weight of
goods)
selective dye added, the machine heated to 190 F at a rate of 5 F per
minute, the
temperature held for 60 minutes, the bath dropped, garments rinsed with warm
water for 5
minutes two times, softener added, water extracted, and the garments dried at
140 F for 40
minutes. Other methods of using selective dyes in the wet processing step are
possible.
Application of the polymer to woven and knitted fabrics.
[0044] There are a vast number of iterations of how this chemistry can be
applied to
produce new and innovative products to meet the many fashion and environmental
needs of
the market. In a woven finishing plant, fabric can be dyed in a number of
ways. These
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include but are not limited to: thermosol dyeing on a continuous dye range or
tenter frame,
pad steaming on a continuous pad/steam range or flash ageing machine, jet
dyeing, jigger
dyeing, beam dyeing, pad/dry/thermosol dyeing, and printing. Fabric can also
be dyed using
a high pressure steamer in which superheated steam is used to achieve
temperatures
approaching 220 F. This technology offers new design and merchandising
opportunities that
can create unique and fashion forward fabric and garment concepts. The
embodiments
presented herein address many of the performance deficiencies inherent in many
products on
the market today, and provides significant environmental advantages to the
current processes.
A number of these ideas are advanced below. The general process is as follows:
[0045] 100% cotton or Polyester/cotton blended fabric in greige form is
received and
is desized, scoured, bleached, and/or mercerized and readied for dyeing. These
processes can
be performed to provide an absorbent, dyeable fabric.
[0046] The prepared fabric is padded with the dye binding composition
comprising
the polymer to achieve a polymer percent solids concentration of between 0.5%
and 10%
solids. In one embodiment, the polymer percent solids concentration is between
2.0% and
7.5% and is calculated as described above.
[0047] Fabric is dried using one or more methods including predryers,
tenter frames,
dry cans, forced air ovens, electric elements, microwave energy or a
combination of the same.
This drying step will cause a film to form. Curing of the polymer will result
at between 250
and 320 F.
[0048] Once the polymer is cured, dye can be applied by pad/roll/extract.
Fixation of
the dye to the polymer can be accomplished for polyester dyes by steaming at
212 to 219 F
for 30 seconds to 3 minutes or thermosol dyeing at between 380 and 425 F for
30 to 45
seconds depending on the dye selection. For the condition in which a cationic
material is
incorporated into a polymeric matrix, the pad/steam option using acid dyes or
selectively
reactive dyes at pH levels below 5.0 can be incorporated.
[0049] Fabric can be dyed by other methods; however, care must be
exercised to
avoid abrasion in fabric form unless this is desired for novel effects in
garment form. In this
case, dyeing could be accomplished in a dye jet. In the case of knits, this is
the preferred
method of dye application other than in garment form. If a soft flow jet is
used such as a
Gaston County FUTURAO or other similar machine, knits can be dyed with a
minimum
amount of abrasion in fabric form.
[0050] One additional dyeing method particularly valid for this approach
is that of
jigger dyeing. Jigger dyeing has the advantage of allowing dye to be applied
to fabric in
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batches by the continuous rolling and rerolling of fabric from one side of the
machine to the
other with dye liquor exchange occurring during the transferring process. This
process
allows for the heating of dye liquor, keeps the liquor to fabric ratio low,
and allows for
evenness of dyeing as long as too much excess dye is not incorporated into the
bath. There
are a finite number of dye sites available within the polymer matrix thereby
limiting the depth
of shade. For this application, dye selection is important in controlling the
shade. Efforts to
match strike rates of the selective dye onto the polymer have been found to
dictate whether
shade continuity can be controlled from one lot to the next.
[0051] In one embodiment, the dyeing process is not conducted in fabric
form for
fabric in which the color is to be applied in garment form.
[0052] The dyed fabric can now be finished by padding softeners onto the
fabric,
framing to width while drying, and removing residual shrinkage through the
sanforization
process.
[0053] Once garments are constructed, wet processing can follow thereby
creating a
garment with abrasion at the seams and highs and lows of color in the flat
areas of the
garment.
[0054] Environmental attributes of this process specifically when
applying the
mixture to yarns prior to weaving have demonstrated that biodegradable
materials in the
entire process can be reduced between 80 and 90 percent. Furthermore, water
and energy use
can be reduced between 50 and 70 percent to achieve comparable-appearing
garments after
wet processing steps in garment form.
[0055] Additional application methods and embodiments of this technology
include
that with the selection of the targeted polymeric urethanes or urethane
mixtures, it is possible
to combine the urethane mixture and dye in a single mixture and subsequently
apply this to a
fabric substrate. The dye has been shown to congregate with the urethane
mixture in solution
and migrate with the urethane during drying leaving the fiber below undyed.
This is
specifically demonstrated when the substrate is cotton or when the dye has a
greater affinity
for the polymeric mixture than the substrate.
[0056] Further, the addition of a fluorochemical produces a fabric with
excellent
water repellant properties; however, the resulting treated substrate is
difficult to dye by
conventional continuous dyeing methods. Adding the dye with the urethane
mixture and the
fluorochemical successfully produced a colored, water repellent, dyed
substrate. This process
was successful in treating para and meta aramids, olefins, cotton, and blends
as outlined
above.
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[0057] When these polymeric urethanes have UV inhibitors added and are
applied to
light sensitive materials such as KEVLARO or other para-aramid and NOMEXO or
other
meta-aramid fibers, not only is the durability of the material improved, but
the material can
be dyed on the surface.
[0058] Application of polymeric urethanes and mixtures in multiple
application and
drying steps have demonstrated that the depth of shade can be enhanced up to
125% when
compared to a single application at the same polymeric solids loading.
[0059] There are numerous variations of this process that can result in
unique fabrics
and garments with enhanced performance characteristic and/or design interests.
Some have
been outlined in the Examples.
Examples
Example #1 (Treatment of Woven Fabrics)
[0060] An 8.2 oz/yd2 3x1 left hand twill 100% cotton fabric with a greige
construction of 108 ends per inch x 56 picks per inch was desized, scoured,
bleached and
mercerized. A solution containing 3% solids was prepared by the addition of 6%
of the dye
bonding composition (the 50% total solids content resulting from the
combination of 45%
solids aqueous polyurethane and 5% solids cellulose acetate) and water at 80
F. The fabric
was padded through a mangle with a hard rubber roll and steel roll with a
pressure set at 40
psi. The fabric wet pickup was 88% resulting in solids add on to the fabric of
2.6%. The
fabric was processed through an 8 zone gas fired tenter at 40 yards per minute
with each zone
set at 380 F. The fabric was completely dried and cured at the exit of the
tenter frame.
Example #1A (Dyeing of treated fabric in garment form)
[0061] Mock pant legs were prepared and laundered as follows: 2.0 kg of
treated
pant legs were loaded into a 35 pound Milnor sample machine. 30 liters of
water were added
to the machine resulting in a 15:1 liquor to goods ratio. The pH was adjusted
to 4.0 by the
addition of 10 ml of acetic acid. DIANIXO Lum Yellow 10G (0.8% OWG) and
DIANIXO
Lum Red 4B-E (0.2% OWG) were diluted in 1 liter of hot 160 F water and
stirred for 2
minutes to disperse the powdered dyes into solution. The dyes were added to
the bath while
the garments were being agitated. The washer was heated at a rate of 5 F per
minute until
reaching 180 F. The machine was held at this temperature for 1 hour before
dropping the
water, rinsing, and applying 10 ml of Ampak Softener Flekes, a cationic
softener. A
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fluorescent orange color resulted and only slight abrasion evidenced by a
slight difference in
color was observed at the seams.
Example #1B (Dyeing treated fabric in garment form adding an abrasive
material)
[0062] 1.0 Kg from Example #1A and 1.0 kg of diatomaceous earth were
added to a
35 lb Milnor machine and processed for 1 hour with a 20:1 liquor to goods
ratio at 80 F.
There was only marginal abrasion at the seams. The garments were rinsed and 1
kg of
pumice stones was added and the process repeated for 30 minutes. Excellent
abrasion was
observed at the seams and the pant leg hems. The fabric was abraded and hairy,
so the
garments were laundered for an additional 20 minutes with a cellulase acid
enzyme at 125 F.
Garments were heated to 160 F with soda ash to deactivate the enzyme, rinsed,
and
additional softeners added at 120 F and a pH of 4.5. The garments were then
extracted,
dried, and reviewed. Abrasion at the seams was clearly evident, the pant leg
hand was soft,
and the white cotton could be clearly seen at the highly abraded points. One
side of the leg
was then hand sanded and feathering was possible simulating wear. This result
clearly
demonstrated the ring dyed property imparted from this dye bonding composition
and
subsequent processing.
Example #1C (Dyeing of treated fabric in fabric form on a pad/steam range)
[0063] Fabric from Example #1 was processed in the lab through a dye bath
containing 10 grams/liter of DIANIXO Royal Blue CC (pH of 4.0 adjusted with
acetic
acid).
[0064] The pad steam range provided a dwell time of 50 seconds at a
steamer
temperature of 218 F. Fabric was rinsed, extracted, and dried on a hot head
press. A
medium royal blue fabric resulted. 1.0 kg of pant legs were loaded into an 80
pound Milnor
sample washing machine. 75 liters of water and 3.0 kg of pumice stone were
added as an
abrasive. The garments were processed at 80 F for 40 minutes, rinsed, and
processed with
1.2% OWG (on weight of garments) of an acid enzyme (SEYCOZYME TCEO) Sydel
Wooley & Company a pH of 4.0 at 125 F for 20 minutes to remove the surface
hairs, the
acid enzyme denatured as previously described, rinsed twice, softened as
described above,
extracted, and dried at 140 F for 40 minutes. The resulting pant legs were a
royal blue shade
and displayed abrasion at the seams exemplified by a loss of color in those
areas. The fabric
was tested for lightfastness, colorfastness, and ozone fading. The
washfastness (American
Association of Textile Chemists and Colorists test method "AATCC" 61 2A)
results showed
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some staining on nylon and acetate and almost no staining on cotton and
polyester fibers.
The shade change was between a 3.0 and 3.5 rating.
Example #1D (Sublimation Printing of treated Woven fabric)
[0065] Treated fabric from Example #1 was selected. A transfer paper was
printed
with color from four dot matrix printers with low energy disperse dyes. The
printed paper
was placed on the fabric face, heated to 400 F by passing the paper and
fabric sandwich over
heated steel rollers. The printed design was transferred to the polymer on the
fabric surface.
Fabric was laundered through five AATCC 135 III Ai cycles (machine wash warm
with 105
F water, dry at hot temperature) to access color retention. Less than 25% of
the color was
lost. Some abrasion of the fabric was observed.
Example #2 (Treatment of previously dyed fabric)
[0066] An 8.2 oz/yd2 3x1 left hand twill 100% cotton fabric with a greige
construction of 108 ends per inch x 56 picks per inch was desized, scoured,
bleached, and
mercerized. This fabric was continuously dyed into an almond yellow color
using a three dye
reactive dye combination. This fabric was cut into 1 yard 12 inch strips for
lab processing.
[0067] A solution containing approximately 3% solids was prepared by
adding 6% of
dye bonding composition (50% solids) with 0.5% TINUVINO 622 from CIBAO
Chemical
Company and water at 80 F. The dyed fabric was padded through a lab padder
set at 40 psi
resulting in a fabric wet pickup of 90%, and dried with predryers and dry
cans.
[0068] A dye bath containing 5 gram/liter DIANIXO Orange SG and 02.0
grams/liter
DIANIXO Red CC was prepared by diluting 5 grams DIANIXO Orange SG and 2.0
grams
of DIANIXO Red CC dye to 1.0 liter and adjusting the pH to 4.0 with acetic
acid. Dye was
padded onto the fabric resulting in a wet pickup of close to 100%. After
steaming the fabric
for 40 seconds at 212 F, washing and drying of the dyed fabric completed the
process. Only
the surface of the fabric was dyed to a chestnut brown color. When the fabric
was cut or torn,
the center of the fabric was clearly still the almond color.
[0069] Fabric swatches were assembled into miniature pant legs with seams
characteristic of 5 pocket jean construction. 1.0 kg of chestnut brown and 4.0
kg of white
bull denim ballast garments were loaded into an 80 pound Milnor sample washing
machine.
75 liters of water and 2.5 kg of pumice stone added as an abrasive. The
garments were
processed at 80 F for one hour, rinsed twice, softened as described above,
extracted, and
dried at 140 F for 40 minutes. The resulting garments had the almond color
showing
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through on the seams and slightly in the flat areas of the mock pant legs
resulting in an
antique looking garment.
Example #3 (Yarn Dyeing to produce blue and colored denim fabric)
[0070] An 8/1 rough spun ring spun yarn was selected for treatment. 1.0
kg of the
yarn was scoured and bleached and 1.0 kg of the yarn was used as spun. A
mixture
comprising the dye bonding composition containing 3% solids was prepared using
the
urethane polymer previously described and water at 80 F. The solution was
padded onto
each yarn using a single end size application apparatus. A wet pickup of the
scoured and
bleached yarn was 120% resulting in a solids add-on of 3.6%. The wet pickup of
the
untreated yarn was 90% resulting on a solids add-on of 2.7%. Both samples were
dried by
passing through a forced hot air oven at 100 m/min for 3 minutes at 90 degrees
C. Both yarns
were smooth to the touch.
[0071] Denim fabric was woven by inserting 50 and 58 picks per inch picks
of the
treated yarn in the filling direction across a 4.5/1 100% cotton warp with 32
ends/inch in a
3x1 left hand twill construction. The fabric width was 59 inches off the loom.
Example #3A (Denim fabric colored during the laundering process)
[0072] Garments were constructed without further processing. In
constructing pant
legs and a garment for color evaluation, the pattern markers were rotated 90
so that the
treated yarn was in the lengthwise direction of the pant leg. Prior to
construction into
garments, the fabric was heated to 325 F for 3 minutes to ensure that the
polymer was
sufficiently cured.
[0073] 5.0 kg of pant legs were loaded into an 80 pound Milnor sample
washing
machine. 75 liters of water (15:1) were added and 15 ml of acetic acid used to
adjust the pH
to 4Ø 100 g of DIANIXO Blue UN-SE (2.0% OWG) was prediluted into 1.0 liters
of 160 F
water before adding to the washer. The temperature was increased at 5 F per
minute until
reaching 180 F. After holding for one hour at 180 F, the water was emptied
and the
garments rinsed at 120 F for 5 minutes through two rinses. 50 grams of Ampak
Softener
Flekes were added to soften the garments. The garments were extracted and
dried at 160 F
for 50 minutes. The finished pant legs had a denim-like appearance with
abrasion
characterized by areas in which there was little or no color at the seam
areas, pockets, and
waist band. The dye did not stain the untreated cotton filling yarns or the
fiber underneath
the polymer matrix.
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Example #3B (Denim fabric colored with multiple colors)
[0074] Example #3A was repeated except instead of dyeing a blue denim
color,
orange, red, fluorescent yellow, and green colors were dyed using the dye
combinations in
Table 1:
Table 1
Dye Formulations for Producing Colored Denim
Amount Total Dye
Color Dye Name
% OWG % OWG
Orange DIANIXO Orange UN-SE 01 1.00 1.00
Red DIANIXO Red UN-SE 1.50 1.50
Fluorescent Yellow DIANIXO Lum Yellow 10G 0.75 0.75
Green DIANIXO Blue UN-SE 1.50
1.75
DIANIXO Lum Yellow 10G 0.25
Example #3C (Denim fabric dyed prior to constructing garments)
[0075] Fabric from Example #3 was taken and cut in the width direction
into 12 inch
strips 59 inches long. A dye bath was prepared by diluting 20 grams of DIANIXO
Blue UN-
SE in one liter of 120 F water. The pH was adjusted to 4.0 by adding 1.0 gram
of acetic
acid. Fabric was padded through the dye solution and steamed for 40 seconds at
212 F,
rinsed through boxes at 160 F, and dried in a forced air oven. The same
fabric was padded
through an identical dye bath as above, dried on pre-dryers and dry cans, and
heated to 400
F for 30 seconds. Mock pant legs were constructed and laundered at 80 F for
60 minutes
with 1 g/1 non-ionic surfactant and rounded pumice stones in a 35 pound Milnor
washer to
enhance abrasion. The bath was dropped, refilled, softener added, heated to
120 F for 5
minutes, extracted and dried. The resulting mock pant legs had abrasion at the
seams and a
denim-like appearance with negligible staining of the untreated cotton fiber.
Example #4 (Application of dye to fibers that are difficult to dye)
[0076] Cut resistant gloves constructed from a composite yarn containing
DYNEEMAO (super high molecular weight polyethylene manufactured by DSM Dyneema
LLC) and nylon. Garments were weighed and prepared for treatment. Previous
efforts to
color this undyeable fiber were met with failure.
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[0077] A bath was prepared by mixing 300 grams of the dye bonding
composition
comprised of a 50% solids urethane solution to 5 liters of 80 F water
creating a 3% solids
solution. lkg of garments were dipped into the bath and soaked for 1 minute.
The garments
were removed, extracted, and 40% of the urethane solution remained. The
garments were
dried at 160 F for 30 minutes in a gas fired drier. Treated garments were
dyed as follows:
[0078] 19 liters of water at 80 F and 1 kg of treated garments were
added to a 35
pound Milnor machine. 10 grams of DIANIXO Lum Yellow lOg (1% OWG) were added
to
200 grams of water at 160 F to solubilize the powdered dye before adding to
the bath. 80
grams of Fluorescent pigment dye (Trichromatic ¨ Tricotex FL Yellow) was
diluted with
800 ml of 80 F water and added to the bath. The mixture was heated at a rate
of 5 F per
minute until reaching 160 F and held at temperature for 30 minutes. The bath
was dropped,
the garments rinsed twice with cold water, and then the garments extracted and
dried for 30
minutes at 140 F. The garments were Fluorescent Yellow in color and showed
excellent
color retention after five wash/dry cycles.
Example #5
[0079] An 8.2 oz/yd2 3x1 left hand twill 100% cotton fabric with a greige
construction of 108 ends per inch x 56 picks per inch was desized, scoured,
bleached and
mercerized. A solution containing 4.1% solids was prepared by the addition of
6.9% of the
dye bonding composition consisting of the urethane material and water at 80
F. 10 linear
yards of fabric 12 inches in width was padded in the lab through a mangle at a
nip pressure
set to 20 psi. The fabric wet pickup was 72% resulting in solids add on to the
fabric of 3.0%.
The fabric was processed by passing the fabric through a forced air oven set
at 375 F for 2
minutes and 5 seconds. With this treated fabric, a number of dyes were
evaluated for
colorfastness, lightfastness, and dye durability. Dye was applied by padding
and squeezing
excess dye from the fabric achieving a wet pickup of around 75%. Fabric was
steamed for 50
seconds at 218 F with saturated steam. Dyed fabric was rinsed with hot 165 F
water and
0.01% surfactant to remove excess dye. Fabric was dried and colorfastness
performance
assessed. Results of a number of dyes evaluated have been illustrated below in
Table 2:
Table 2
Evaluation of Dyes for Fastness and Performance
Dye Name Concentration Colorfastness Testing
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(g/1)
120 F Washfastness Crocking Ozone Lightfastness FadGains g
AATCC
AATCC
AATCC 61-2A AATCC 8 AATCC 16
109 23
Shd
Chg Cotton Polyester Dry Wet 2-
cycles 20 hours 1-cycle
DIANIXO Lum Yell
5.0 3.5 4.5 4.5 2.5 2.5 4.0 1.0 5.0
10-G
DIANIXO Yellow S-
5.0 1.5 4.5 4.0 3.5 3.5 3.0 4.5 3.0
4G
DIANIXO Orange S-
10.0 3.5 3.5 4.5 3.5 3.5 2.5 4.5 4.0
DIANIXO Yellow
10.0 3.5 4.0 4.5 3.5 3.5 2.5 4.5 4.5
Brn CC
DIANIXO Lum Red
10.0 1.5 3.5 4.5 3.5 3.5 1.5 1.0 1.5
DIANIXO Cyanine B 10.0 1.5 4.5 4.5 3.5 3.5 1.5 1.0
2.0
DIANIXO Blue BG 10.0 4.5 3.0 4.0 4.5 4.0 1.0 4.5
2.5
DIANIXO Rubine CC 5.0 3.5 2.0 3.0 4.0 3.0 1.5 3.0
4.0
[0080] For assessing performance of the tested material, grading is done
on a scale of
1.0 to 5Ø A rating of 1.0 indicates significant color change; a rating 5.0,
no color change.
Ratings of 3.5 and above are generally considered good. For the dyes listed
above, several
would be unsuitable for this application. A dye that has poor washfastness
such as
DIANIXO Lum Red G may appear a poor candidate if only assessing washfastness;
however, if a fluorescent red is required, this dye may be the only option
available. For dyes
with poor lightfastness, chemical additives can be incorporated into the
polymeric mixture to
improve performance. For dyes with poor ozone fastness, materials are
available after wet
processing that can improve this performance. Dyes assessed in this fashion
have been
selected as candidates for this process.
Example #5A - Dyeing with multiple techniques
[0081] To assess the impact of dye technique on colorfastness
performance, the
treated fabric was processed in three ways in the lab and the colorfastness
properties
assessed:
Dye Process 1: 10 g/1 dye padded, steamed, washed, and dried.
Dye Process 2: 10 g/1 dye padded, predryed, can dried, and thermosol dyed at
416 F
for 50 seconds, washed, and dried.
Dye Process 3: Dye Process 1 & Thermosol dyed at 416 F for 50 seconds,
washed,
and dried) on the same piece of fabric.
[0082] Colorfastness results are depicted in Table 3.
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Table 3
IMPACT OF DYE PROCESS ON COLORFASTNESS
Trial Description Disperse Colorfastness Testing
of Dye Navy GFE 120 F Washfastness Crocking Lightfastness
Method Concentration AATCC 61-2A AATCC 8 AATCC 16
(g/l) Shd Cotton Polyester Dry Wet 20 hours
Chg
Dye Pad Steam 10.0 3.0 4.5 3.0 4.5 2.5 4.5
Process
#1
Dye Pad 10.0 3.0 3.5 2.0 4.5 2.5 3.0
Process Thermosol
#2
Dye Pad Steam 10.0 3.0 3.5 2.5 4.5 2.5 2.0
Process / Pad
#3 Thermosol
[0083] The first two techniques were successful at producing an
acceptable dyeing.
The pad steam option appears to provide the best lightfastness and
washfastness result likely
from minimizing dye staining of the untreated cotton and keeping excess dye
from the fabric
surface.
Example #6 - Treatment of cotton Stretch Fabrics
[0084] A 7.8 oz/yd2 3x1 Left Hand Twill 99/1 Cotton/Spandex fabric with a
finished
construction of 109 ends per inch x 50 picks per inch comprising a 20/1 Ring
Spun Warp and
a 10/1 open end + 14/1 + 70 denier spandex filling was prepared by a desize,
caustic scour,
bleach, mercerize process before dyeing. The fabric was processed by applying
a urethane
mixture adjusted to a pH of 5.8 with acetic acid with 4.1 percent solids. A
wet pickup of 72%
resulted in a solids pickup on the fabric of 3.0 percent. Moisture was reduced
to about 45%
before the fabric was dried and cured on dry cans.
Example #6A
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[0085] Fabric was dyed into a multitude of shades on a pad steam range.
Preliminary
work in the lab revealed that at a 3.0% chemical application level, most
medium shades were
able to be matched. One color selected was Spiced Orange. The dye formulation
contained:
TABLE 4
Spiced Orange
Dye Auxiliary Concentration
(grams/liter)
DIANIXO Scarlet CC 10.0
DIANIXO Orange SG 2.0
Barasol (surfactant) 0.5
Acetic Acid (20%) 0.2
[0086] Fabric was processed at 75 yards per minute by applying the Spiced
Orange
dye formulation through a Kuster pad with a measured pickup of 75%. The dyes
were fixed
after processing through a tight laced steamer at 216 F for 50 seconds. Very
little excess dye
was observed during the washing process. The fabric was dried, finished, and
sanforized to
remove shrinkage.
[0087] The fabric was tested for a number of physical and colorfastness
performance
parameters as depicted below. Washfastness performance was better before than
after
finishing. The chemical formulation in finishing is likely the cause. Fabric
was made into
garments and wet processed. Washfastness performance improved after wet
processing with
only a 15 to 20% reduction in shade except on the seams and hand sanded areas.
TABLE 5
Physical Test Results - Spiced Orange
Attribute Test Method Test Result Units
Weight ASTM D-3776 7.35 oz/yd2
Width 64.5 inches
Construction ASTM D-3775 Ends Picks per inch
128 52
Tensile ASTM D-5034 Warp Filling
169 77 lbs
Elmendorf Tear ASTM D1424 6.6 7.2 lbs
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Seam Slippage ASTM D-434 54 55 lbs
Needle cutting ASTM D-1906 0 4 Cuts
Shrinkage AATCC 135 IVAi -2.45 -7.4 percent
Stretch & Growth ASTM D-3107 Growth Stretch
Initial 1.3 10.6 percent
After 3 launderings 5.6 17.5 percent
Pilling (Random Tumble) ASTM D-3512 30 60 minutes
4.0 3.0 Grade
TABLE 6
Colorfastness Test Results - Spiced Orange
Attribute Test Method Test Result Units
Washfastness AATCC 61-2A Shade Chg Cotton Polyester Grade
After dyeing 4.0 3.5 4.0
After Finishing* 3.5 2.5 2.5
After Garment Wash 4.0 4.0 4.5
Perspiration* AATCC 15 4.5 4.0 4.0 Grade
Cold Water Bleeding* AATCC 107 4.0 3.5 4.5 Grade
Crocking* AATCC 8 Dry Wet Grade
4.0 2.5
Gas Fading* AATCC 23 4.5 1 cycle Grade
Lightfastness* AATCC 16 3.5 20 hours Grade
Ozone* AATCC 109 4.5 2 cycles Grade
*After fmishing test results
Example #6B ¨ Wet processing of Spiced Orange Garments
[0088]
Fabric was constructed into a womenswear jean cut in a size 6. Four sets of
garment increments, each set consisting of three garments and weighing 1.0 kg,
were
processed to evaluate the impact of wash procedure on overall appearance and
aesthetic.
The wash procedures included:
A) A Rinse Wash ¨ 20 minute wash at 120 F with softener
B) A 20 minute Enzyme Wash ¨ A 20 minute wash at 125 F with acid enzymes
followed by a 10 minute softening step at 120 F Softening step
C) A 20 minute Stonewash + 20 minute Enzyme Wash ¨ A 20 minute wash at 100 F
with a 2:1 Pumice Stone to garment ratio followed by a rinse, a 20 wash at 125
F
with acid enzymes followed by a 10 minute softening step
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D) A 40 minute Stonewash + 20 minute Enzyme Wash ¨ A 40 minute wash at 100 F
with a 2:1 Pumice Stone to garment ratio followed by a rinse, a 20 wash at 125
F
with acid enzymes followed by a 10 minute softening step
[0089] The rinse wash was effective at softening the fabric hand and
little to no
abrasion was observed. The color appeared similar to that of a garment
constructed from a
piece dyed fabric. In several garments, the thigh portion of the garment was
presanded prior
to laundering. In all cases, these sanded areas appeared lighter and worn with
white, undyed
cotton apparent in the more heavily sanded areas. Garments that were enzyme
washed for 20
minutes had a shade drop of about 10% and a slight bit of abrasion on the side
seams, belt
loops, and bottom hems of each leg. The sanded areas were clearly lighter than
the unsanded
areas.
[0090] Adding stonewashing to the process provided an abraded look
generally seen
in ring dyed or surface dyed fabrics. The abrasion was greater after 40
minutes than 20 and
both garments had excellent abrasion without any significant destruction to
the integrity of
the garment. Generally, to achieve a comparable abraded appearance in similar
garments
using classical dyeing techniques, more than twice the stone washing is
required and physical
damage to the garment is generally observed.
[0091] The areas of the garments that were hand sanded prior to
stonewashing were
nearly white in the more heavily sanded areas. This color differentiation
results because the
dyes selected do not redeposit on the fabric once in solution during
processing. Finally, after
the garments were processed, softened, and dried, additional highlights could
be readily
created by hand sanding after wet processing. This ability adds a new
dimension to the
options available to the wet processor and the designer looking for new and
innovative
garments.
Example #7 ¨ Yarn Treatment of 100% cotton and the environmental impact
[0092] A raw 20/1 Ring Spun 100% cotton warp comprised on 4260 ends was
processed through a box containing a urethane mixture consisting of 9% solids.
After the
yarn was dipped and excess material removed with squeeze rolls set at 45 psi,
a wet pickup of
105% was measured resulting in a 9.45% solids add on to the yarn. Each yarn
was separated
while wet and dried at 150 F for 50 seconds followed by steam cans set at 275
F to ensure
that the fabric is dry and the polymeric matrix cured. Under these conditions,
no steam was
observed on the cans indicating that the yarn was completely dry before
reaching the cans.
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Treated yarn was wound onto a loom beam and woven on a Picanol air jet loom.
Fabric was
woven at 71 inches with 60 ends per inch and 60 picks per inch in a plain
weave construction
to produce a fabric that once dyed, would produce a chambray effect. The
chambray effect is
exemplified by a plainweave construction less than 6 oz/yd2 in which only the
warp or
lengthwise yarn is dyed and the filling yarn remains white. Chambray is
generally seen in
indigo colors in which the warp yarns have been dyed on an indigo dye range.
Colored
chambrays are generally not available because of dye minimums, the ability to
match color,
and the associated expense. Chambrays produced from this invention can be
prepared by
scouring and bleaching the treated fabric through normal preparation
processes. Absorbancy
of prepared fabric was less than one second from the time a drop of water
touches the fabric
surface to when it dissipates. The whiteness of treated and untreated fabric
after preparation
cannot be differentiated.
Example #7A ¨ Preparation and dyeing of treated yarn
[0093] Fabric from Example #7 is scoured on a continuous bleach range by
applying
a scouring formulation comprising 4% sodium hydroxide solution with EDTA type
chelating
agents (ethylene diamine tetra-acetic acid) with an alkaline stable surfactant
system. The
scouring process was completed by steaming the fabric for 10 minutes and
rinsing. The
fabric was then bleached with a bleaching formulation comprising hydrogen
peroxide,
sodium hydroxide, an organic stabilizer and a chelating agent for 25 minutes
before being
washed and dried. It is important to note that the dye binding composition
disclosed herein
unexpectedly permits this process of scouring and bleaching to occur without
loss of dye
quality on the material. In contrast, dyeing procedures known in the art would
result in
extensive loss of dye on the material if processed with a scouring and
bleaching formulation.
[0094] Fabric was dyed a navy color on a steam range at 75 yards/min
using a
formulation consisting of 7.0 g/liter DIANIXO Navy CC and 2.0 g/liter of Black
CA-B with
a KUSTERO pad with a 75% WPU. The dyes become fixed by passing the fabric
through a
tight laced steamer at 216 F for 50 seconds and then washing. The fabric
produced from this
trial was a fabric with chambray appearance and aesthetic produced using 100%
cotton yarn.
This is achieved by selecting dyes that do not dye cotton so only the coating
on the warp
yarns become dyed. Efforts to minimize dye staining of the cotton have been
achieved
through rigorous washing after the steamer. The colorfastness performance and
specifically
the lightfastness performance is a function of the effectiveness of removing
surface dye from
the untreated cotton portion of the blend. The initial lightfastness of this
trial tested in
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accordance with AATCC 16-E after 20 hours was 1.5. The same dye formulation on
a solid
fabric treated sample has an initial lightfastness of 3.5. Additional washing
with special
soaps enabled the lightfastness performance to improve to between a 2.5 and
3.0, depending
on the amount of fugitive dye remaining. As the lightfastness performance
improved, so also
did the overall washfastness. Prepared fabric was dyed in the lab in a variety
of colors
including yellows, oranges, blues, violets, tans, khakis, greens, browns,
plums, and greys.
The significance of this process is:
1) Large number of colors are possible
2) Shade matching can be done quickly
3) Minimums become less problematic
4) Wash down of fabric remains on hue
5) Significant environmental impact
Example #8 ¨ The environmental impact
[0095] Based
on wet processing results from fabrics from Examples #3 and #7, and
upon procedures well established in the industry used in the production of
washed-down
indigo denim jeans, the environmental impact of each was determined.
Conditions including
prescouring, bleaching, yarn dyeing, and wet processing of finished garments
were a part of
the assessment. With the indigo denim, an assumption was made that the wet
processing
would include desizing, permanganate spraying, bleaching, abrasion with
neutral cellulase
enzymes and an abrasive material, softening, and drying. From the results in
Table #7, the
impact of this invention on the environmental footprint of wet processing is
significant.
TABLE 7
The Environmental Impact of Urethane Mixture
Indigo Blue Jeans versus Urethane Produced Colored Denim
Total processing (fabric through finished garment) Indigo Urethane Difference
% Reduction
Biodegradable materials (% by weight) 10.8 2.4 8.4 78
Alkali (% by weight) 8.0 5.0 3.0 38
Chlorine (% by weight) 3.0 0.0 3.0
100
Heavy Metals (Manganese ppm) 700 0 700
100
Wet processing in garment form
Indigo Urethane Difference % Reduction
Time (min/garment) 1.68 0.97 0.71 42
Energy (Kcals/garment) 1259 528 731 58
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fl Water (gallons/garment) 13.47 5.17 8.3
62 I
[0096] Table #7 is illustrative of the impact of the invention on
biodegradable waste
products associated with textiles in general, and denim specifically.
Processing of Indigo
denim garments generally requires the removal of a sizing material generally
in the form of
starch. This alone represents around 6% of the total weight of the denim.
Amylase and
cellulase enzymes, cellulose, and dye round out the remaining percentage. The
majority of
the material removed from the Urethane processed fabric results from cellulose
degradation
promoted by cellulase enzymes. This results in nearly an 80% reduction of
biodegradable
solids when compared with normal processing. The aesthetic character of the
Urethane
processed fabric or yarn is achieved without the use of typical oxidative
materials like
hypochlorite bleaches or potassium permanganate materials. This eliminates the
need for
heavy metals like manganese in the process. Finally, most wet-processing can
be done at
lower temperatures with fewer rinses resulting in a 40 to 60% reduction of
time, water, and
energy to process garments incorporating this technology.
Example #9 ¨ Impact of chemical concentration on the depth of shade and
processes to
achieve shades when greater dye uptake is desired
[0097] During the development process, there appeared to be a limit to
the amount of
dye that the urethane material can incorporate into the surface matrix. This
level was thought
to be dependent upon the concentration of urethane solids applied to the
fabric. Application
of solids at the 3.0%, 5.0%, and 6.5% levels revealed that there was little to
no benefit of
increased solids on depth of color with the application technique of chemical
mixture
described in Example #5. There was a linear effect of color build for all four
chemical level
applications when dye concentration was increased from 5 grams per liter to 15
grams per
liter when evaluating DIANIXO Blue S-BG. (See FIG. 1). When solids are applied
in
multiple steps of application/cure, the dye yield doubles at 5% solids and
increases 250% at
6.5% solids. This increased color yield enables darker colors to be realized.
[0098] In FIG. 1, the standard strength is set to 100% for the lightest
swatch. All
swatches are compared to that lightest swatch. For all of the dyeings made
from fabric that
had a single application of chemical, dye yield was fairly linear up to 15 g/1
and an increase
from 5.0 g/1 to 15 g/1 resulted in an 80% increase in strength.
[0099] When additional chemical solids are applied in a second pass, two
results
occur: first, the slope of the dye yield changes with increased dye
concentration from an 80%
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strength increase, to 140%. Second, the dye yield for the two pass application
with 5.0%
solids nearly doubles and in the case for the two pass application with 6.5%
solids, the depth
of shade increases 2.5 fold.
[00100] When greater depth of shade is desired, fabric may be processed by
a dual
pass method.
Example #10 ¨ Treatment of fabric with specialized yarns to achieve a vintage
appearance
after wet processing with pumice stones.
[00101] A 10.8 oz/yd2 98/2 cotton spandex with a greige construction of 80
ends per
inch x 46 picks per inch and a finished construction of 93 ends per inch and
48 picks per inch
comprising an Amsler Ring Spun 9.75 warp yarn and a 10/1 + 70 denier spandex
was
prepared by desizing, scouring, bleaching, and mercerizing the fabric. The
Amsler spinning
technique creates yarn that mirrors much of the inconsistency in yarn
prevalent before
sophisticated yarn production techniques creating uniform yarn were
introduced. The Amsler
spinning technique creates slubs in the yarn. This fabric was treated as
described in Example
#5. Fabric was dyed as described in Example 5A ¨ Dye Process #1 through a pad
steam
range through a dye formulation consisting of 10 g/1 of DIANIXO Blue S-BG. The
dyed
fabric was thoroughly washed, dried, and constructed into denim-like pant
legs. The legs
were laundered in a Washex 250 lb machine with pumice stones for 50 minutes at
90 F to
assess the impact of the stones on the seams and on the slub portion of the
Amsler warp
yarns. The resulting laundered pant legs demonstrated excellent abrasion at
the seams and
the thick places on the uneven warp yarns. Negligible coloration of the cotton
yarn
underneath the abraded high points in the yarn was observed. (When laundering
indigo
denim, this problem is a major concern). After drying, the resultant pant legs
were somewhat
hairy from the abrasive effect of the pumice stones. Some additional hand
sanding was done
to demonstrate an even greater contrast between the slubs and the surface of
the fabric. A
modified technique was used to assess stretch and growth by leaving one of the
seams in the
pant leg to provide sufficient length in the filling to do the measurements.
Other than this
modification, the laundered garment was tested in accordance with ASTM D-3107.
Stretch
was 24% and growth was 5.2%.
Example #11 ¨ Combination of treated and untreated yarns to create novel
selvedge designs
for denim and chambrays
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[00102] 16 ends of 20/1 from the yarn treated from Example #7 were taken
and
combined with 12 ends of 20/1 yarn from fabric that had been desized, scoured,
bleached,
and mercerized. The yarns were configured across a 12 inch template
approximately 0.5 mm
apart from one another with 6 treated yarns, followed by 6 untreated yarns,
followed by 2
treated yarns, 6 untreated yarns and 6 treated yarns for a total of 28 yarns.
A 16/1 Ring spun
yarn that had been scoured, bleached, and mercerized was woven in a plainweave
construction with 30 yarns per inch. Two inches were woven with a needle by
hand. The
tails of the ribbon were sewn to leader fabric and processed through a pad
steam as described
in Example #5A ¨ Dye Process #1. The dye formulation consisted of 7.0 g/1 of
DIANIXO
Blue S-BG. The resulting 2 inch ribbon was about one half inch. Where the
untreated warp
yarn and white filling yarn were together, two white stripes with a fine dyed
stripe resulted.
This clearly demonstrated that stripes will be possible to create when fabric
is continuously
dyed with the appropriate dyes. Some staining on the white yarn was observed;
however, a
clear contrast was demonstrated between the treated and untreated yarn.
Example #12 ¨ Treatment of Flame resistant fabrics imparting color to fibers
difficult to dye.
[00103] A 55/45 Protex C modacrylic/combed cotton 6.9 oz/yd2 plainweave
woven
fabric was desized, scoured, and bleached prior to treatment. Fabric was
treated as described
in Example #5. Fabric was dyed to produce a bright firehouse red shade with
the pad steam
process described in Example #5A-Dye Process #1 using the attached
formulation:
Table 8
Firehouse Red
Concentration
Dye Auxiliary
(grams/liter)
DIANIXO Rubine CC 5.0
DIANIXO Orange SG 1.0
Barasol (surfactant) 0.5
Acetic Acid (20%) 0.2
[00104] Fabric was tested for vertical flammability. The results indicated
that the
addition of the urethane did not change the after flame and char length
performance when
tested in accordance with ASTM D-6413 initially and after three launderings in
accordance
with AATCC 135 IV-Ai. (120 F with detergent). This is the same laundering
procedure
used to assess dimensional stability in the warp and filling directions. Char
length in both
warp and filling direction were less than 4 inches and afterflame was less
than 0.5 seconds.
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As described in this example, application of the treatment to KEVLARO was
successful in
producing a red shade; however, the color was much more yellow than the protex
Cl cotton
blend because of the differences in color of the treated substrate. The
KEVLARO was
golden yellow before treatment and red orange after treatment. Based upon the
results from
the dyeing of these materials separately, a 50/40/10 Protex C/Combed
Cotton/para-aramid is
being constructed and will be dyed this same red shade for potential
commercial use.
Example #13 ¨ Treatment of polypropylene
[00105] A 30 inch 4.0 oz/yd2 plain weave woven fabric with 24 ends and 24
picks
comprised of 625 denier polypropylene yarns was treated by padding a urethane
mixture
containing 4.1 percent solids through a mangle set at 20 psi. A wet pickup of
60 percent was
measured resulting in a solids add on to the substrate of 2.5%. Fabric was
dried and cured in
a dispatch oven at 180 F for 5 minutes. Fabric was dyed as described in
Example #5A ¨
Dye Process #1 with the following formulation producing a saturated Gray
shade.
Table 9
Gray
Dye Auxiliary Concentration
(grams/liter)
DIANIXO Black CA-B 5.0
Barasol (surfactant) 0.5
Acetic Acid (20%) 0.2
[00106] Exemplary embodiments include:
[00107] A denim-like fabric and garment comprised of cotton or
cotton/synthetic fiber
produced from the application of a dye bonding composition comprised of a
mixture of
polymers of the urethane, guanidine, and vinyl halogen families with or
without additives that
sequester dye in which the polymer combination is preferentially dyed over the
cellulosic
fiber. The preferential dyeing of the polymer combination over the cellulosic
fiber produces
ring dyed yarns that can subsequently be abraded in garment form.
[00108] In some embodiments of the denim-like fabric and garment, yarn or
fabric is
dyed prior to, during, or after the fabric is woven with dyes that are not
substantive to the
cellulosic material. In this embodiment, the dyes do not have the propensity
of reacting with
or sticking to cellulose. In the case in which the dye bonding composition is
comprised of a
urethane alone or mixed with a cellulose ester, selective dyes such as
disperse dyes are
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preferred. In the case in which the dye bonding composition is comprised of a
urethane
combined with guanidine creating a cationic polymer, acid or reactive dyes of
the vinyl
sulfone or monochloro hydrazine family that also stain cotton can be used. In
the case in
which polyester is blended with cotton in these blends, using a cationic
polymer is the
preferred approach.
[00109] In some embodiments of the denim-like fabric and garment, the dye
bonding
composition comprises a urethane emulsion polymer blended with powdered
cellulose acetate
in a urethane emulsion polymer to powdered cellulose acetate ratio ranging
from 90:10 to
50:50 or a urethane emulsion polymer to powdered cellulose ratio ranging from
90:10 to
75:25. This blend is contained in an aqueous solution containing 50% solids
which is further
diluted prior to application to yarn, fabric, or garments.
[00110] The fabric and garment can be dyed in yarn form, fabric form, or
garment
form with selective dyes that have preferential attraction to cellulose
acetate and/or the
urethane polymer.
[00111] In some embodiments, a process by which fiber, yarn, fabric, and
garments
can be produced through the application of a dye bonding composition
comprising at least at
least one polymer, wherein the dye bonding composition is preferentially dyed
over the
cellulosic fiber, producing ring dyed yarns that can subsequently be abraded
in garment form
is provided.
[00112] In some embodiments of the process, the yarn or fabric is dyed
prior to,
during, or after the fabric is woven with dyes that are not substantive to the
cellulosic
material. In the case in which the dye bonding composition is comprised of a
urethane mixed
with a cellulose ester, selective dyes are preferred. In the case in which the
dye bonding
composition is comprised of a urethane combined with guanidine creating a
cationic polymer,
acid or reactive dyes of the vinyl sulfone or mono chloro hydrazine family
that also stain
cotton can be used. In the case in which polyester is blended with cotton in
these blends,
using a cationic polymer is the preferred approach.
[00113] In some embodiments, the process includes dyeing cotton knit or
woven
fabrics varying in weight from 3 to 14 oz/yd2 with reactive, sulfur, vat, or
naphthol dyes to
precolor the substrate. Subsequently, the dye bonding composition is applied
as described
above, and then the cured dye bonding polymer matrix is dyed a different color
with selective
dyes that affix to the polymer matrix but do not color or stain the dyed color
underneath the
polymer. The dyeing of the polymer can be done in garment form or fabric form.
Fabric can
be dyed by jigger, pad/dry/thermosol, pad/steam, and/or jet dyed. The garments
produced
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from this process are abraded during wet processing with various abrasive
materials including
pumice stones, sand, plastic abrasive balls, etc., resulting in garments that
have abrasion at
seams, back pockets, hems, and the like that allow the original color to show
through creating
tonal effects.
[00114] In further embodiments, the process includes applying the dye
bonding
composition comprised of the urethane polymer material to fibers, yarns,
fabrics, or garments
which contain materials difficult to dye including DYNEEMAO, KEVLARO,
polybenzamidazole (PBI), PBOO and blends thereof, providing a film on the
surface of the
materials to which dye binders can attach. This dye bonding composition can be
dyed with
selective dyes and the polymeric matrix can further be dyed with pigments and
other
colorants that adhere through the action of acrylic and other binding
polymeric materials.
[00115] While certain exemplary embodiments have been described and shown
in the
accompanying drawings, it is to be understood that such embodiments are merely
illustrative
of and not restrictive on the broad invention, and that this invention not be
limited to the
specific constructions and arrangements shown and described, since various
other updates,
combinations, omissions, modifications and substitutions, in addition to those
set forth in the
above paragraphs, are possible.
[00116] Those skilled in the art may appreciate that various adaptations
and
modifications of the just described embodiments can be configured without
departing from
the scope and spirit of the invention. Therefore, it is to be understood that,
within the scope
of the appended claims, the invention may be practiced other than as
specifically described
herein.
33
