U.S. patent application number 15/846182 was filed with the patent office on 2018-04-19 for ring dyed materials and method of making the same.
The applicant listed for this patent is Randolph L. Finley. Invention is credited to Randolph L. Finley.
Application Number | 20180105978 15/846182 |
Document ID | / |
Family ID | 54189523 |
Filed Date | 2018-04-19 |
United States Patent
Application |
20180105978 |
Kind Code |
A1 |
Finley; Randolph L. |
April 19, 2018 |
RING DYED MATERIALS AND METHOD OF MAKING THE SAME
Abstract
A ring dyed textile product resulting from the treatment of
yarn, fabric, or garments with a combination of a dye, engineered
polymer, and heat. The resulting material can be engineered into
fabric, garments, or other textile product. Subsequent abrasion of
the article can produce apparel in a broad color range that has an
aesthetic appearance similar to that of garments produced from
indigo dyed yarn. Colorfastness performance including crocking,
washfastness, and lightfastness are good to excellent for a broad
color range.
Inventors: |
Finley; Randolph L.; (Fort
Myers, FL) |
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Applicant: |
Name |
City |
State |
Country |
Type |
Finley; Randolph L. |
Fort Myers |
FL |
US |
|
|
Family ID: |
54189523 |
Appl. No.: |
15/846182 |
Filed: |
December 18, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14242281 |
Apr 1, 2014 |
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15846182 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D06P 1/5285 20130101;
D06P 1/5257 20130101; D06P 1/6735 20130101; D06P 1/38 20130101;
D06P 5/2077 20130101 |
International
Class: |
D06P 1/38 20060101
D06P001/38; D06P 1/52 20060101 D06P001/52 |
Claims
1. A ring dyed yarn comprising: a polymer-dye matrix positioned
adjacent to an outer portion of the yarn, the polymer-dye matrix
comprising a polymer layer and a reactive dye entrapped within the
polymer layer.
2. The ring dyed yarn of claim 1, wherein the polymer layer
comprises at least one of a urethane based polymer and an acrylic
polymer.
3. The ring dyed yarn of claim 2, wherein the urethane based
polymer has a glass transition temperature (Tg) of -65.degree. C.
to 70.degree. C.
4. The ring dyed yarn of claim 1, wherein the reactive dye
comprises at least one of triazine derivatives, pyridimine
derivatives, quinoxaline derivatives, and activated vinyl
compounds.
5. The ring dyed yarn of claim 1, wherein the yarn comprises at
least one material selected from the group consisting of cotton,
polyamide, wool, polyester, meta-aramids, polyproplylene,
polyethylene, para-aramids, and modacrylics.
6. The ring dyed yarn of claim 1, wherein an inner portion of the
yarn is substantially free of the reactive dye.
7. The ring dyed yarn of claim 1, wherein an inner portion of the
yarn comprises a dye that is different from the reactive dye.
8. A ring dyed fabric comprising: a polymer-dye matrix positioned
adjacent to an outer portion of the fabric, the polymer-dye matrix
comprising a polymer layer and a reactive dye entrapped within the
polymer layer.
9. The fabric of claim 8, wherein the fabric comprises at least one
of a denim-like woven fabric construction, a non-woven fabric, and
a knit fabric.
10. The fabric of claim 8, wherein the fabric comprises at least
one of cellulosic fibers and synthetic fibers.
11. The fabric of claim 8, further comprising a flame retardant
agent.
12. The fabric of claim 8, wherein the polymer layer comprises a
urethane based polymer having a glass transition temperature (Tg)
from about -50.degree. C. to about -20.degree. C.
13. The fabric of claim 8, wherein the percent solids on fabric
ratio of polymer to reactive dye is at least 1:1.
14. The fabric of claim 8, wherein the fabric has a dry crocking of
greater than 3.5 and a wet crocking of greater than 2.5 in
accordance with AATCC Test Method 8.
15. The fabric of claim 8, wherein the fabric has a lightfastness
of greater than 3.0 at 20 hours and a lightfastness of greater than
2.5 at 40 hours in accordance with AATCC Test Method 16A.
17. The fabric of claim 8, wherein the fabric comprises an abraded
fabric such that one or more surface areas of the fabric are
substantially free of the polymer-dye matrix.
18. The fabric of claim 8, wherein the fabric further comprises a
post treatment additive comprising an emulsified wax.
19. A ring dyed garment comprising: a fabric; a polymer-dye matrix
positioned adjacent to an outer portion of the fabric, the
polymer-dye matrix comprising a polymer layer and a reactive dye
entrapped within the polymer layer.
20. A method of producing a ring dyed substrate, the method
comprising: providing a substrate; depositing a polymer-dye
composition on at least a portion of the substrate, the polymer-dye
composition comprising an aqueous mixture of one or more polymers
and a reactive dye; heating the treated substrate such that the
polymer-dye composition moves to the surface of the substrate;
depositing an alkaline salt mixture on the substrate; and forming a
polymer-dye matrix positioned adjacent to an outer portion of the
substrate in response to the alkaline salt mixture deposition, the
polymer-dye matrix comprising a polymer layer and a reactive dye
entrapped within the polymer layer.
21. The method of claim 20, wherein the substrate comprises at
least one of a yarn or fabric.
22. The method of claim 21, wherein an inner portion of the yarn is
substantially free of the reactive dye.
23. The method of claim 21, further comprising: depositing a dye
mixture comprising a second reactive dye on the yarn or fabric; and
producing a two-toned fabric as a result of the deposit, wherein an
inner portion of the yarn comprises the second reactive dye and
wherein the yarn is substantially free of the first reactive
dye.
24. The method of claim 20, wherein the substrate comprises a
previously dyed substrate.
25. The method of claim 20, wherein the substrate is subjected to
at least one of desizing, scouring, bleaching, and mercerization
prior to treatment.
26. The method of claim 20, wherein the polymer is cured in
response to the heating.
27. The method of claim 20, further comprising: abrading at least a
portion of the outer portion of the substrate to remove at least
some of the polymer-dye matrix such that the substrate has first
surface areas comprising fibers that comprise the reactive dye and
second surface areas comprising fibers that do not include the
reactive dye.
28. The method of claim 20, further comprising: depositing a post
treatment additive comprising an emulsified wax on at least a
portion of the substrate.
Description
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 are challenges.
[0002] Attempts to create "ring dyed" yarns have resulted in
lengthy processing and poor performance. The most common and
prevalent technique is that of indigo dyeing 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.
[0003] Ring dyeing has been further attempted with the application
of pigment dyes mixed with binders. This approach has resulted in
fabric with stiff handle and marginal rub-fastness performance.
Even with advances to improve performance, color choice and depth
of shade versus rub fastness performance remain challenging.
SUMMARY
[0004] 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.
[0005] In a first embodiment, a ring dyed yarn is provided, where
the ring dyed yarn includes a polymer-dye matrix positioned
adjacent to an outer portion of the yarn, the polymer-dye matrix
comprising a polymer layer and a reactive dye entrapped within the
polymer layer.
[0006] In a first aspect of the first embodiment, the polymer layer
comprises at least one of a urethane based polymer and an acrylic
polymer.
[0007] In a second aspect, alone or in combination with the first
aspect of the first embodiment, the urethane based polymer has a
glass transition temperature (Tg) of -65.degree. C. to 70.degree.
C.
[0008] In a third aspect, alone or in combination with any of the
previous aspects of the first embodiment, the reactive dye
comprises at least one of triazine derivatives, pyridimine
derivatives, quinoxaline derivatives, and activated vinyl
compounds.
[0009] In a fourth aspect, alone or in combination with any of the
previous aspects of the first embodiment, the yarn comprises at
least one material selected from the group consisting of cotton,
polyamide, wool, polyester, meta-aramids, polyproplylene,
polyethylene, para-aramids, and modacrylics.
[0010] In a fifth aspect, alone or in combination with any of the
previous aspects of the first embodiment, an inner portion of the
yarn is substantially free of the reactive dye.
[0011] In a sixth aspect, alone or in combination with any of the
previous aspects of the first embodiment, an inner portion of the
yarn comprises a dye that is different from the reactive dye.
[0012] In a second embodiment, a fabric is provided, where the
fabric a polymer-dye matrix positioned adjacent to an outer portion
of the fabric, the polymer-dye matrix comprising a polymer layer
and a reactive dye entrapped within the polymer layer.
[0013] In a first aspect of the second embodiment, the fabric
comprises at least one of cellulosic fibers and synthetic
fibers.
[0014] In a second aspect of the second embodiment, alone or in
combination with the first aspect of the second embodiment, the
fabric comprises at least one of a denim-like woven fabric
construction, a non-woven fabric, and a knit fabric.
[0015] In a third aspect, alone or in combination with any of the
previous aspects of the second embodiment, the fabric includes a
flame retardant agent.
[0016] In a fourth aspect, alone or in combination with any of the
previous aspects of the second embodiment, the polymer layer
comprises a urethane based polymer having a glass transition
temperature (Tg) from about -50.degree. C. to about -20.degree.
C.
[0017] In a fifth aspect, alone or in combination with any of the
previous aspects of the second embodiment, the percent solids on
fabric ratio of polymer to reactive dye is at least 1:1.
[0018] In a sixth aspect, alone or in combination with any of the
previous aspects of the second embodiment, the fabric has a dry
crocking of greater than 3.5 and a wet crocking of greater than 2.5
in accordance with AATCC Test Method 8.
[0019] In a seventh aspect, alone or in combination with any of the
previous aspects of the second embodiment, the fabric has a
lightfastness of greater than 3.0 at 20 hours and a lightfastness
of greater than 2.5 at 40 hours in accordance with AATCC Test
Method 16A.
[0020] In an eighth aspect, alone or in combination with any of the
previous aspects of the second embodiment, the fabric comprises an
abraded fabric such that one or more surface areas of the fabric
are substantially free of the polymer-dye matrix
[0021] In a ninth aspect, alone or in combination with any of the
previous aspects of the second embodiment, the fabric further
comprises a post treatment additive comprising an emulsified
wax.
[0022] In a third embodiment, a garment is provided, where the
garment includes fabric and a polymer-dye matrix positioned
adjacent to an outer portion of the fabric, the polymer-dye matrix
comprising a polymer layer and a reactive dye entrapped within the
polymer layer.
[0023] In a fourth embodiment, a method of producing a ring dyed
substrate is provided, the method comprising providing a substrate;
depositing a polymer-dye composition on at least a portion of the
substrate, the polymer-dye composition comprising an aqueous
mixture of one or more polymers and a reactive dye; heating the
treated substrate such that the polymer-dye composition moves to
the surface of the substrate; depositing an alkaline salt mixture
on the substrate; and forming a polymer-dye matrix positioned
adjacent to an outer portion of the substrate in response to the
alkaline salt mixture deposition, the polymer-dye matrix comprising
a polymer layer and a reactive dye entrapped within the polymer
layer.
[0024] In a first aspect of the fourth embodiment, the substrate
comprises at least one of a yarn or fabric.
[0025] In a second aspect, alone or in combination with the first
aspect of the fourth embodiment, the inner portion of the yarn is
substantially free of the reactive dye
[0026] In a third aspect, alone or in combination with any of the
previous aspects of the fourth embodiment, the method further
includes depositing a dye mixture comprising a second reactive dye
on the yarn or fabric; and producing a two-toned fabric as a result
of the deposit, wherein an inner portion of the yarn comprises the
second reactive dye and wherein the yarn is substantially free of
the first reactive dye
[0027] In a fourth aspect, alone or in combination with any of the
previous aspects of the fourth embodiment, the substrate comprises
a previously dyed substrate.
[0028] In a fifth aspect, alone or in combination with any of the
previous aspects of the fourth embodiment, the substrate is
subjected to at least one of desizing, scouring, bleaching, and
mercerization prior to treatment.
[0029] In a sixth aspect, alone or in combination with any of the
previous aspects of the fourth embodiment, the polymer is cured in
response to the heating
[0030] In a seventh aspect, alone or in combination with any of the
previous aspects of the fourth embodiment, abrading at least a
portion of the outer portion of the substrate to remove at least
some of the polymer-dye matrix such that the substrate has first
surface areas comprising fibers that comprise the reactive dye and
second surface areas comprising fibers that do not include the
reactive dye
[0031] In a fifth embodiment, a chemical composition for a ring
dyed material is provided, where, the composition includes a
urethane based polymer and a reactive dye preferentially attracted
to the urethane.
[0032] 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
[0033] 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:
[0034] FIG. 1 is a diagram illustrating a process for preparing a
ring dyed substrate, in accordance with an embodiment of the
disclosure;
[0035] FIG. 2A is a cross-sectional view of the fiber in FIG. 1 at
one stage of the process in accordance with the various
embodiments;
[0036] FIG. 2B is a cross-sectional view of the fiber in FIG. 1 at
one stage of the process in accordance with the various
embodiments;
[0037] FIG. 2C is a cross-sectional view of the fiber in FIG. 1 at
one stage of the process in accordance with the various
embodiments;
[0038] FIG. 3 is a front elevation view of a fabric and enlarged
view of a portion of the fabric in accordance with the various
embodiments;
[0039] FIG. 4 is a front elevation view of a fabric and enlarged
view of a portion of the fabric in accordance with the various
embodiments; and
[0040] FIG. 5 is a block diagram illustrate a process of producing
a ring dyed substrate in accordance with the various
embodiments;
DETAILED DESCRIPTION
[0041] 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.
[0042] 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.
[0043] Some dye systems generally incorporate pigments with acrylic
polymers to create colored materials. As the depth of color
increases, a greater amount of acrylic polymer is needed to secure
the color to the substrate being colored. In many cases, this
adversely affects the fabric handle and generates colorfastness
performance issues of crocking (color transfer when the article is
rubbed), and washfastness when the fabric is laundered. When
attempting to apply pigment color to individual yarns with acrylic
binders, the moisture regain and resultant tacky characteristic of
the system make this approach difficult to commercialize. The
embodiments presented herein overcome these difficulties.
[0044] The embodiments are directed to ring dyed textiles,
polymer-dye compositions, and methods of producing the same. A
polymer-dye composition comprising at least one polymer is
provided. In some embodiments, the polymer-dye composition
comprises at least one urethane polymer. The urethane polymer can
be an emulsion polymer and have a low glass transition temperature
(Tg) in the range of, for example, about -65.degree. C. to about
70.degree. C. Low Tg urethanes provide good flexibility and
aesthetic fabric handle. In some embodiments, the Tg of the
urethane polymer ranges from about -50.degree. C. to about
-20.degree. C. In particular embodiments, the Tg of the urethane
polymer is -42.degree. C.
[0045] In some embodiments, the polymer-dye 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. 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.
[0046] 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.
[0047] 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
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.
[0048] 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.
[0049] 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.
[0050] In other embodiments, the polymer-dye composition comprises
one or more acrylic polymers. Although acrylic co- and ter-polymer
systems, without careful engineering, may exhibit poorer migration
properties and hand aesthetic characteristics than urethane
materials, acrylic polymers have yielded promising results in the
entrapment of reactive dyes.
[0051] In particular embodiments, the polymer-dye composition
includes a reactive dye. Exemplary reactive dyes include triazine
derivatives, pyridimine derivatives, quinoxaline derivatives, and
activated vinyl compounds.
[0052] Reactive dyes can include three components: a chromophore
that dictates the color, solubilizing groups that aid in the dye
dissolving in an aqueous environment, and one or more reactive
moieties. The reactive moieties are responsible for enabling the
dye to form covalent bonds between the dye chromophore and hydroxyl
groups on cellulosic fibers. There are a number of reactive
moieties that are available to enable bonding to occur including:
vinyl sulphone, monochlorotriazine, monfluorotriazine,
difluorocholorpyrimidine, dechlorotriazine, dichloroquinoxaline,
trichloropyrimidine, and vinyl amide. In many cases, several of
these reactive moieties are engineered into a dye structure to
maximize the probability that a dye will form a permanent bond with
the fiber. As described herein, dyes containing bis vinyl
sulphones, bis fluorotriazines, vinyl sulphones, and/or
monochlorotrazine/vinyl sulphones moieties have been all shown to
have excellent lightfastness, colorfastness and color retention
characteristics.
[0053] A multitude of fiber and fiber blends that can be treated
include cellulosic and plant based fibers such as cotton, linen,
flax, hemp, rayon, flame resistant rayon, and their derivatives;
natural fibers such as silk and wool; synthetic fibers such as
polyethylene (e.g., DYNEEMA.RTM., a super high density
polyethylene), polypropylene, aliphatic polyamides, para- and
meta-aramids (e.g., KEVLAR.RTM. and NOMEX.RTM.), modacrylics,
and/or blends of these materials and 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.
[0054] Referring now to the figures, FIG. 1 illustrates a process
100 for producing a ring dyed yarn. Although a yarn is illustrated,
it will be understood that the process 100 can also be applied to
fabrics and garments. A first stage yarn 110A treated with the
polymer-dye composition is provided. FIG. 2A illustrates a
cross-sectional view of the first stage yarn 110A. The area 200
comprises the fibers of the yarn, which is saturated with the
polymer-dye mixture.
[0055] Returning to FIG. 1, the first stage yarn 110A undergoes a
drying step in which the yarn 110A is subjected to heat.
[0056] As shown in FIG. 1, the application of heat results in
second stage yarn 110B. In an aqueous mixture of urethane polymer
and a reactive dye, the dye is attracted to the urethane. As heat
is applied to the surface of the substrate, the reactive dye and
urethane polymer migrate together to the surface portion leaving
little or no dye and/or polymer in the center of the yarn
structure. The heat causes the water to evaporate from the treated
material and the polymer/dyestuff matrix of the polymer to cure.
The polymer/dye matrix on the surface portion of the substrate
results in a ring-dyed yarn, fabric, or garment.
[0057] FIG. 2B shows the cross-sectional view of the second stage
yarn 110B. A polymer-dye matrix area 210 forms as the composition
migrates toward the surface or outer portion of the yarn 110B
leaving substantially no polymer-dye composition in an inner core
area 212 of the yarn 110B. In the illustrated embodiment, the core
area 212 comprises only the yarn fibers and not the polymer-dye
composition.
[0058] Referring again to FIG. 1, the second stage yarn 110B is
then subjected to a fixation step. To fix or otherwise attach the
reactive dye to the surface, the second stage yarn 110B is treated
with a salt brine/alkali mixture that causes the reactive dye to
become insolubilized or attached to bonding sites within the
urethane matrix to produce a third stage yarn 110C. One possible
outcome of this treatment is that the reactive dye becomes
insolubilized and is not easily removed from the polymer matrix.
The urethane polymer or polymer system can be engineered to contain
hydroxyl groups either in the urethane system or through the
addition of other polymeric materials to which the dyes can form
covalent bonds. It will be understood, however, that the hydroxyl
groups are not required for fixation to occur.
[0059] FIG. 2C illustrates a cross-section view of the third stage
yarn 110C. On the outside of the yarn 110C is a fixed dye-polymer
portion 214. The fixed dye-polymer portion 214 is positioned
adjacent to the surface or outer portion of the yarn and surrounds
at least a portion of the core area 212. In some embodiments, the
fixed dye-polymer portion 214 comprises the polymer-dye matrix
described herein and is contact with the outer surface of the yarn
110C such that there is no space between the yarn surface and the
polymer-dye matrix. The fixed dye portion 214 is insolubilized and
entrapped within the polymer portion 216.
[0060] Treated yarn or fabric can be constructed into knitted,
woven, or non-woven substrates and converted into garments. FIG. 3
illustrates a fabric 300 that includes a ring dyed yarn 320 (e.g.,
a yarn produced by the process 100 described above) in the warp
direction and untreated filling yarns 310. In the illustrated
embodiment, the fabric 300 is a 3.times.1 Left Hand Twill woven
denim fabric. The ring dyed yarn 320 includes an outer dyed portion
322 and an inner non-dyed portion 324.
[0061] FIG. 4 illustrates a fabric 400 comprising a 3.times.1 Left
Hand Twill woven denim fabric after a laundering process with
pumice stones. Abrasion of the fabric or garment surface from
sanding, stone washing, or other means, removes the polymer/dye
coating such that the fiber color underneath is exposed. The fabric
400 includes ring dyed yarns 420 in the warp direction that have
been abraided and untreated filling yarns 410. The ring dyed yarns
420 include an outer dyed portion 422 that has been abraided and an
inner non-dyed portion 424.
[0062] Experiments have revealed that without the alkali/salt brine
treatment, the initial durability of the reactive dye is poor with
more than 50% of the color removed when the substrate is laundered
at low temperatures.
[0063] Additional experiments that involve applying, drying, and
curing only the polymer to the fabric without the dye in the
mixture, have also been conducted. When reactive dye is applied and
dried to this treated substrate and subsequent dye fixation
attempted with an alkali/salt brine solution, color fixation was
not observed on the urethane polymer because the polymer did not
have any sites available for reaction with the reactive moieties of
the reactive dye. In experiments where the polymer was engineered
with receptor sites for the dye, color fixation was observed. In
other cases where hydroxyl rich material is incorporated with the
urethane polymer system without the dye in the mixture, and
subsequently applied to fabric, dried, cured, and then treated with
reactive dye and fixed with the alkali/salt brine, the dye reacts
with the groups on the surface of the fabric or fiber. However,
poor light fastness, crocking, and rubbing are observed in these
cases.
Mix Preparation with Polymer and Reactive Dye
[0064] In one method for the application of color, the polymer-dye
compositions is applied to a substrate in a single bath, the coated
substrate is then dried, the polymer-dye composition cured, and
then the dye is fixed to the substrate with alkali.
[0065] A water based urethane mixture can be prepared having about
0.5% to about 10% solids depending upon the weight of the fabric or
the size of the yarn to which it is being applied. In some
embodiments, the urethane mixture has 2.5% to 6.0% urethane solids.
A mineral based defoamer can be added should foam generation during
processing become a problem. Reactive dye is generally added to the
polymer mixture after pre-dilution. In further embodiments, one or
more reactive dyes are added to the aqueous urethane mixture in a
concentration range from about 0.01 g/l to 70 g/l. Because the
majority of the dye migrates to the fabric surface, concentrations
can be 25% to 30% less than the amount typically needed to color
cellulose based materials (1 g/l to 100 g/l). The ratio of urethane
solids to reactive dye can affect performance. The dried polymer
range on the surface of the substrate, in some embodiments, is
equal to or greater than 2.5% solids on fabric. In this way, a
satisfactory surface coating of polymer is achieved. This polymer
loading can easily support 1.5% to 2.0% dye concentrations without
adversely affecting colorfastness performance. As a greater depth
of color is desired, additional polymer can be added to the
formulation as additional dye is added.
Treatment and Drying of the Polymer/Dye Mixture onto Yarn, Fabric,
or Garments
[0066] FIG. 5 illustrates a schematic diagram of a production
assembly 500 for producing a ring dyed substrate. Untreated yarn
510 yarn is dipped into a bath 520 of the polymer-dye composition
and then squeezed through a squeeze roller set 530 to remove excess
liquid. In other embodiments, a previously dyed yarn can be used.
Although the illustrated embodiment depicts dipping, other
application methods include foaming, kiss coating, or printing. In
some embodiments in which the dipping method is employed, wet
pickup levels between about 45% and 250%, depending on the fiber
blend and absorbency of the yarn, are achieved. Percent wet pickup
is calculated as the [(fabric wet weight after padding)-(fabric dry
weight before padding)]/(fabric dry weight before padding)*100.
Prior to treatment of fabric, fabric can be prepared through a
number of processes including desizing, scouring, bleaching, and/or
mercerizing to enhance absorbency and whiteness of the fabric.
Should a base color other than white be desired, fabric can be dyed
prior to treatment.
[0067] The polymer-dye composition can be applied to a number of
materials comprised of fibers including cotton, polyester, acetate,
rayon, jute, wool, modacrylic, nylon, super high density
polyethylene (SHDPE), polypropylene, para-aramids (KEVLAR.RTM.,
TWARON.RTM.), meta-aramids (NOMEX.RTM., CONEX.RTM.), cotton and
cellulosic blends containing durable flame resistant polymers
including ammonia treated tetrakis hydroxyl methyl phoshonium
chloride urea precondensate or dialkylphosphonocarboxylic acid
amide, and the like. Any mixture of fibers can be spun into yarns,
and the fibers can be treated in yarn, fabric, or garment form.
Flammability performance is not negatively affected by the
polymer-dye composition, and fabric can be dyed after the flame
retardant treatment. Colorfastness performance is excellent at
elevated temperatures while lightfastness performance is dyestuff
dependent.
[0068] After the yarn is run through the squeeze roller set 530,
hot air is applied to the yarn via driers 540A and 540B positioned
above and below the assembly line. The application of hot air
allows the polymer-dye composition to migrate to the surface
portion of the yarn and the water to evaporate from the yarn. The
yarn can be dried by heating the yarn with, for example, infrared
heat, hot air, dry cans, microwave, or a combination of these
methods. To achieve a ring-dyed appearance, it is necessary to
apply enough heat to the surface of the yarn so that the
dye-polymer composition migrates to the surface as the water
evaporates. In cases where an even coloration is desired, an even
application of heat to the treated yarn can be applied because
water tends to migrate towards heat. Spotty heat treatment can
result in uneven color distribution. After the water has been
evaporated, the dye-polymer composition forms a film and the dye
becomes trapped within the film matrix.
[0069] The yarn can then be repackaged for further treatment as
described below. In the illustrated embodiment, the treated yarn is
wound onto a spool 550.
[0070] In other embodiments, the dye-polymer composition is applied
by padding and subsequently squeezing the excess from the fabric
with a mangle. Application can also be achieved with foam
application, kiss roll mixture transfer, or printing
techniques.
[0071] In addition, the dye-polymer composition is applied to
garments (dyed or white) by spraying to a wet pickup of 70% to 250%
of the weight of the garments, drying, fixing the dye with alkali
through additional spraying or dipping techniques, and subsequently
wet processing the treated garments with abrasive pumice stones to
remove the polymer/dye matrix from the surface particularly at
seams and sewn areas of the garment. The garments can be enzyme
washed to create a smoother, cleaner surface and softeners can be
added to enhance the garment handle.
[0072] In particular embodiments, the polymer-dye composition is
applied to at least a portion of a fabric using a Kusters pad,
which allows control of chemical and dye application across the
width of the fabric for shade consistency. Once the polymer/dye
amalgam has been applied to the fabric, drying and curing of the
polymer film can be achieved on a tenter frame, infrared driers,
dry cans, hot flue oven, roller oven, microwave, or a combination
of these methods. Fabrics can be dried at temperatures that promote
the drying of water. In some embodiments, fabric surface reaches at
least 240.degree. F. This temperatures range ensures that the
polymer film is completely cured. Fabric temperatures above
350.degree. F. are not detrimental to the polymer, but may cause
yellowing of the fabric or poor stretch and growth performance of
the fabric after treatment if spandex is in incorporated into the
fabric.
Fixation of the Dye
[0073] Once the dye/polymer mixture has been applied to the yarn,
the dye can be fixed to the yarn and the yarn can be incorporated
into the warp, filling, or knit depending on how the yarn is
processed. In other cases, the yarn can be first converted into a
fabric before fixation to enhance efficiency. The dye can be fixed
to the substrate by padding the yarn or fabric with a salt brine
mixture containing alkali. Salt brine salt levels in the form of
sodium chloride can range from 80 g/l to 150 g/l. In some
embodiments, the sodium chloride level is in the range of about 100
g/l to 120 g/l based upon a 220% wet pickup. Alkalinity can be
achieved using a multitude of bases. In some cases, sodium
hydroxide and sodium carbonate are used to minimize cost. The
alkalinity levels selected are proportional to the concentration of
reactive dye. Under alkaline conditions, reactive dyes are
activated and either react with available hydroxyl groups to form
covalent bonds or the activated dyes react with water to become
hydrolyzed. When the salt/alkali mixture is introduced to the
urethane polymer/dye matrix, the reactive dye becomes fixed within
the polymeric matrix resulting in excellent fastness
properties.
[0074] The polymer and reactive dyestuff are selected based on
their attraction to one another. For ring dyeing to result, the
polymer is engineered to migrate preferentially with the water to
the surface rather than to be attracted to the fiber and hindered
from migration. Radiant heat can be applied to the surface of the
fabric to encourage migration of water and the polymer-dye
composition to the heated surface because of the motive force
created from the surface evaporation of water. Subsequent fixation
results from the hydrolysis of the dye, which changes the
solubility characteristics of the dye within the matrix. Because
the majority of the polymer-dye matrix is on or near the fabric
surface, the amount of dye required to dye the yarn or fabric is
reduced by between 50% and 75% to achieve comparable colors to
normal reactive dyeings.
[0075] Yarn can be treated to achieve near indigo colors, woven,
and then treated with alkali/salt brine solutions to achieve
indigo-like denim for which only abrasion is necessary to achieve
denim-like appearing garments. This technology extends the color
range from indigo to a broad color range including yellows,
oranges, reds, greens, violets, blue, and colors resulting from the
combination of a broad range of dye combinations.
[0076] The typical environmental issues associated with the
processing of indigo garments includes the initial alkali treatment
and washing of the raw yarn to improve yarn absorbency and removal
of size after the weaving process. The sizing material represents
up to 6% of the weight of the fabric being produced and leads to
large amounts of waste. The embodiments described herein eliminate
the alkali pretreatment and the need for the application and
subsequent removal of sizing material. Once the dye/polymer mixture
is applied and cured on the surface, very little is removed during
and after fixation, so very little dye waste is observed during
processing. In addition, the concentration of dye needed to achieve
medium to dark shades is reduced by 50% to 75%.
[0077] Color removal during wet processing is achieved through the
abrasion of the polymer from fabric surface using multiple abrasion
techniques.
[0078] When only reactive dyes are used to dye cellulosic
materials, penetrative dyeing in which the entire yarn bundle is
dyed typically results and ring dyeing is not readily achievable.
In cases where a cotton fabric is treated and cured with polymeric
material alone; and reactive dyes subsequently applied and fixed
with alkali/salt, the reactive dye has no substantivity for the
polymer unless specific hydroxyl rich material (poly vinyl alcohol
for example) has been introduced to the polymeric matrix prior to
curing. The reactive dyes evenly dye the cotton fiber underneath
the polymer and no color difference is observed between polymer
treated cotton and untreated cotton fabric.
[0079] In the present embodiments, reactive dyes can be quarantined
or preferentially attracted to a polymeric material prior to curing
and fixed to the substrate surface or outer portion of the
substrate with heat leaving little to no dye inside of the cotton
yarn bundle. Furthermore, if the reactive dyes are not fixed with
alkali, a substantial portion of the dye can be easily removed with
washing. The additional fixation step locks the dye beneath the
surface of the polymer and creates exceptional color fastness
properties on a broad range and saturation of color. The polymer
matrix is very effective at holding the majority or all of the dye
in place to allow fixation to occur.
[0080] For fabrics for which bleaching is desired, it has been
found that the fabric can be bleached with hydrogen peroxide
through a cold pad process without adversely affecting color or
polymer integrity. Hydrogen peroxide bleaching can also be done on
the dyed garment with negligible removal of the color of the dyed
yarn. Most color change can result from abrasion of the polymer/dye
matrix rather than actual removal of the dye through the use of
surfactants or alkalinity. Materials that generally degrade
reactive dyes such as hypochlorite bleaches, reducing agents such
as sodium hydrosulfite (sodium dithionite), and strongly oxidative
agents such as potassium permanganate are still effective in
destroying these dyes even when the dyes are trapped in the
polymeric matrix.
[0081] The embodiments described herein result in very little
fugitive dye that otherwise might be available to redeposit on
uncolored yarns. This has been demonstrated after stone washing
and/or enzyme treatment of yarn or fabric that have been treated
with the polymer-dye composition. Washfastness test results on
treated fabrics also confirm a negligible amount of color loss and
color redeposition on most fiber types including acetate, cotton,
nylon-6,6, polyester, orlon, or wool with typical results across a
broad range of dyes of 4.0-5.0 on a grey scale when tested in
accordance with AATCC 613A at 160.degree. F. In addition,
lightfastness (AATCC 16--Option 1) after 40 exposure hours had
ratings of 3.5 or greater on the majority of the selected dyes.
(The grading scale ranges from 1.0 to 5.0 with a 1.0 rating poor
and 5.0 rating excellent). Ozone and Burnt Gas Fading when tested
in accordance to AATCC 109 and AATCC 23 respectively had
performance values of 4.0 or above on all dyes tested.
[0082] This technology can be applied to a multitude of fibers and
fiber blends. Even fibers that typically do not readily accept dyes
have been found to accept color applied through the formation of a
dye/polymer matrix on the surface of the substrate. Examples have
been provided below. These examples are designed to illustrate the
flexibility of the process and resulting ring-dyed products, but
does not limit the scope of applications.
EXAMPLES
Example #1A
Treatment and Ring Dyeing of 100% Cotton Bull Denim--(Urethane+Dye)
No Alkali Fixation
[0083] A 12 oz/yd2 100% cotton 3.times.1 right hand twill fabric
with 74 ends and 42 picks comprised of 8.5/1 Ansler Ringspun warp
yarn and 6.0/1 Open end filling yarn was desized, scoured,
bleached, and mercerized prior to treatment. A Urethane/Dye mixture
was prepared to engineer a 3% urethane solids add on and a 0.72
percent reactive dye concentration by weight based upon a chemical
mixture wet pickup of 72%. In one case, low molecular weight
polyvinyl alcohol (PVA) was added to ensure that the reactive dye
had hydroxyl groups to which covalent bonds could be formed. In the
control case, no PVA was added. The reactive dye selected was
NOVACRON.RTM. Blue CR (Reactive Blue 235). Mix #1, comprised of
urethane and Blue CR was padded onto bull denim and excess chemical
removed with a mangle. The fabric was dried in a Warner Mathis oven
for 90 seconds at 360.degree. F. Formulations for Mix #1 and Mix#2
are provided in Table 1A below.
TABLE-US-00001 TABLE 1A Mix #1 Mix #2 Concentration Solids on
Concentration Solids on Chemical (g/l) fabric (%) (g/l) fabric (%)
Notes Texstream TST-U60 69.00 3.00 69.00 3.00 60% active urethane
Defoamer CH2 1.00 1.00 Mineral based defoamer Novacron .RTM. Blue
10.00 0.72 10.00 0.72 Huntsman CR Chemical Co. Seyco PVA 22.00 0.40
25% active material Note: Chemical Wet Pickup = 72%
[0084] The fabric was washed in four liters of 160.degree. F. water
for 25 seconds; 25 seconds with two liters of 160.degree. F. water
and 1 g/l sulfonated castor oil; and finally rinsed with four
liters of clean 160.degree. F. water and 2.5 g/l of 20% acetic
acid. Excess water was extracted from the fabric before drying on a
hot head press. Approximately 50% of the dye was removed from the
sample.
Example #1B
Treatment and Ring Dyeing of 100% Cotton Bull Denim--(Urethane+Dye)
Alkali Fixation
[0085] The fabric was processed as in Example #1A. Before the
washing step, a mixture of 11.25 g/liter caustic soda, 15 g/liter
soda ash, and 1.08 g/liter salt bring as provided in Table 1B below
was applied to the fabric and processed through a Werner Mathis
steamer at 118.degree. C. with a dwell time of 50 seconds.
TABLE-US-00002 TABLE 1B Fixation Mixture Concentration Chemical
(g/l) Caustic Soda 11.25 (100%) Soda Ash 15.00 Salt (NaCl) 108.00
Note: Chemical wet pickup = 220%
[0086] The fabric was washed as outlined in Example #1A, extracted
and dried. Almost no color was removed in the washing process.
Experiments were repeated with the addition of 0.4% polyvinyl
alcohol solids in the urethane mixture with no appreciable
washfastness performance differences.
Example #1C
Finishing of Dyed 100% Cotton Bull Denim Fabric
[0087] Fabric from Example #1A and Example #1B were finished by
processing the fabric through a pad containing 50 g/l of
PHOTOBEX.RTM. JVA (an emulsified wax, 20% solids). Excess mix was
removed by a mangle and the fabric vacuum extracted to a wet pickup
of 45%. The fabric was dried at 340.degree. F. for 70 seconds and
then tested for colorfastness properties. Washfastness performance
was evaluated using AATCC 61 2A (120.degree. F.) and 3A
(160.degree. F.) protocols. Results have been depicted in Table 1C.
Results were best for the fabrics that had been treated with the
alkali/salt brine solution with negligible shade change or color
transfer after laundering at 160.degree. F.
TABLE-US-00003 TABLE 1C Colorfastness performance of Ring-Dyed 100%
Bull Denim Urethane/Novacron .RTM. Urethane/PVA/Novacron .RTM. Blue
CR (Mix #1) Blue CR (Mix #2) No Alkali/Salt No Alkali/Salt Test
Description Test Method Alkali Brine Alkali Brine Lightfastness (20
hrs) AATCC 16E 4.5 4.5 4.5 4.5 Washfastness AATCC 61 (120.degree.
F.) 2A Shade Change 3.5 4.5 3.0 4.5 Acetate 5.0 5.0 5.0 5.0 Cotton
3.5 4.0 3.5 4.0 Nylon 4.5 4.5 4.5 4.5 Polyester 5.0 5.0 5.0 5.0
Orlon 5.0 5.0 5.0 5.0 Wool 5.0 5.0 5.0 5.0 Washfastness
(160.degree. F.) AATCC 61 Shade Change 3A 3.5 4.5 3.0 4.0 Acetate
5.0 4.5 5.0 5.0 Cotton 3.0 3.5 3.0 3.5 Nylon 4.0 4.5 4.0 4.5
Polyester 5.0 5.0 5.0 5.0 Orlon 5.0 5.0 5.0 5.0 Wool 5.0 5.0 5.0
5.0
Example #1D
Wet Processing of Finished 100% Cotton Bull Denim Pant Legs
[0088] Fabric from Example #1C was crafted into mock pant legs with
a felied seam to mimic seams found in denim pant garments. Pant
legs were laundered in a 65 lb Washex machine with a 2:1 pumice
stone to fabric ratio, 10:1 water to fabric ratio, and a fabric
load level of 10 pounds. The pant legs were wet processed at
100.degree. F. for 60 minutes and then separated from the pumice
stone. The pant legs were then rinsed with water at 120.degree. F.
to remove pumice sand, extracted, and tumble dried at 160.degree.
F. until dry. There was abrasion at the felied seam where the
polymer/dye matrix had been removed leaving untreated, undyed white
highlights. There was no redeposition of the color onto the abraded
white areas typical of indigo and pigment dyes. Colorfastness
properties were measured again and found to be nearly identical to
properties of the fabric before wet processing.
Example #2A
Ring Dyeing of 100% Cotton Bottom Weight Fabric with Multiple
Reactive Dye Colors--Application and Processing
[0089] An 8.7 oz/yd.sup.2 3.times.1 Right Hand Twill 100% combed
cotton fabric with 117 ends and 56 picks comprised of a 30/2 ply
warp and 26/2 ply filling was desized, scoured, bleached, and
mercerized prior to treatment. A series of 12 reactive dyes were
selected and mixtures of each prepared and processed as
follows:
[0090] 1) 1.0 gram of Defoamer CH2 (a mineral based defoamer
available from the Apollo Chemical Company) was added to 200 ml of
water and vigorously stirred.
[0091] 2) 69.0 grams of TST-U60 (60% active urethane) (available
from Texstream Technologies) was added to the water and defoamer
and diluted to 500 ml.
[0092] 3) In a separate container, 10.0 grams of powdered reactive
dye (available from Huntsman Corporation) was added to 250 ml of
140.degree. F. water and stirred until all of the dye had
dissolved. The dye solution was adjusted to a pH of 4.8 to 5.6 with
acetic acid.
[0093] 4) While stirring the urethane mixture, the dye solution was
added. Additional water was added to produce 1.00 liter of
solution.
[0094] 5) A 12 inch wide fabric sample was processed through the
mixture and excess mix removed with a mangle set at 20 psi. A wet
pickup of between 72% and 75% was measured resulting in a urethane
solids add on of approximately 3.0% and a dye concentration of
0.72% to 0.75%.
[0095] 6) Fabric was dried and cured at 360.degree. F. for 90
seconds in a Werner Mathis oven.
[0096] 7) Fabric was processed through a mixture of alkali/salt
brine consisting of 11.25 g/l caustic soda, 15 g/l soda ash, and
108 g/l salt brine (NaCl). A wet pickup of between 225% and 250%
resulted when processing fabric through a pad with no squeezing.
Fabric was steamed at 118.degree. C. for 50 seconds.
[0097] 8) Fabric was rinsed in 4 liters of 160.degree. F. water for
30 seconds. Little to no dye was rinsed from the fabric. Additional
washing was achieved by stirring the fabric in 2 liters of water at
160.degree. F. with 2 grams of sulfonated castol oil for 30 seconds
to remove any soluble dye. A final rinsing in 4 liters of water at
160.degree. F. for 30 seconds completed the washing cycle. The
fabric was extracted and dried on a hot head press.
[0098] 9) Fabric was finished as described above in Example #1C.
Testing was completed on each of the 12 dyes selected and the
results depicted in Tables 2A and 2B1-2B2 below.
TABLE-US-00004 TABLE 2A Colorfastness of Urethane coupled with
Selective Reactive Dyes Test Method AATCC AATCC AATCC 8 AATCC 16A
109 23 Reactive Color Index Concentration Crocking Lightfastness
Ozone Gas Fade Dye Name moities Name (g/l) Dry Wet 20 hrs 40 hrs 2
cycles 1 Cycle Novacron .RTM. MFT-VS Reactive 30 (33% 5.0 5.0 4.5
4.5 5.0 5.0 Yellow C5- Yellow liq) G 179 Novacron .RTM. MFT-
Reactive 10.0 5.0 4.5 5.0 4.5 4.5 4.5 Yellow FN- MFT Yellow 2R
(bis) 206 Novacron .RTM. VS-VS Reactive 10.0 5.0 4.5 4.5 4.5 4.5
4.5 Orange (bis) Orange C3R 131 Novacron .RTM. MFT- Reactive 10.0
5.0 3.5 4.5 4.0 5.0 5.0 Orange MFT Orange FNR (bis) 135 Novacron
.RTM. MCT-VS Reactive 10.0 5.0 4.0 3.5 2.0 5.0 5.0 Red SB Red 264
Novacron .RTM. MCT-VS Proprietary 10.0 5.0 4.5 4.5 4.0 4.5 4.5 Ruby
S-3R (mixture) Novacron .RTM. VS Reactive 10.0 5.0 4.5 4.5 3.5 4.0
5.0 Turquoise Blue 21 GN Novacron .RTM. MFT-MFT Reactive 10.0 5.0
4.0 4.5 3.0 4.5 4.5 Blue C4R (bis) Blue 261 Novacron .RTM. MFT-VS
Reactive 10.0 5.0 4.5 4.5 4.0 5.0 4.5 Blue CR Blue 235 Novacron
.RTM. VS-VS Reactive 10.0 5.0 4.0 4.5 3.5 4.5 4.5 Navy W-B (bis)
Black 5 IN Novacron .RTM. VS-VS Proprietary 10.0 5.0 4.5 4.0 3.5
5.0 4.5 Navy SG (bis) (mixture) MFT = Monoflourotriazine MCT =
Monochlorotriazine VS = Vinylsulphone
TABLE-US-00005 TABLE 2B1 Colorfastness of Urethane coupled with
Selective Reactive Dyes Test Method AATCC 61 2A Washfastness
(120.degree. F.) Shade Dye Name .DELTA. Acetate Cotton Nylon
Polyester Orlon Wool Novacron .RTM. 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Yellow C5-G Novacron .RTM. 4.5 5.0 5.0 5.0 5.0 5.0 5.0 Yellow FN-2R
Novacron .RTM. 4.0 5.0 5.0 5.0 5.0 5.0 5.0 Orange C3R Novacron
.RTM. 5.0 5.0 4.5 4.5 5.0 5.0 5.0 Orange FNR Novacron .RTM. 4.5 5.0
5.0 4.5 5.0 5.0 5.0 Red SB Novacron .RTM. 4.5 5.0 5.0 5.0 5.0 5.0
5.0 Ruby S-3R Novacron .RTM. 4.5 5.0 3.5 4.5 5.0 5.0 5.0 Turquoise
GN Novacron .RTM. 4.5 5.0 5.0 5.0 5.0 5.0 5.0 Blue C4R Novacron
.RTM. 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Blue CR Novacron .RTM. 4.5 5.0
5.0 4.5 5.0 5.0 5.0 Navy W-B IN Novacron .RTM. 2.0* 5.0 5.0 5.0 5.0
5.0 2.0 Navy SG Novacron .RTM. 3.0 5.0 4.5 5.0 4.5 5.0 5.0 Navy
CBN
TABLE-US-00006 TABLE 2B2 Colorfastness of Urethane coupled with
Selective Reactive Dyes Test Method AATCC 61 3A Washfastness
(160.degree. F.) Shade Dye Name .DELTA. Acetate Cotton Nylon
Polyester Orlon Wool Novacron .RTM. 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Yellow C5-G Novacron .RTM. 4.5 5.0 5.0 5.0 5.0 5.0 5.0 Yellow FN-2R
Novacron .RTM. 4.5 5.0 4.5 4.5 5.0 5.0 5.0 Orange C3R Novacron
.RTM. 4.5 5.0 4.5 4.5 5.0 5.0 5.0 Orange FNR Novacron .RTM. 4.5 5.0
5.0 4.5 5.0 5.0 5.0 Red SB Novacron .RTM. 4.5 5.0 5.0 5.0 5.0 5.0
5.0 Ruby S-3R Novacron .RTM. 4.0 5.0 3.5 4.5 5.0 5.0 5.0 Turquoise
GN Novacron .RTM. 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Blue C4R Novacron
.RTM. 5.0 5.0 4.5 5.0 5.0 5.0 5.0 Blue CR Novacron .RTM. 4.0 5.0
5.0 4.5 5.0 5.0 5.0 Navy W-B IN Novacron .RTM. 2.0* 4.0 5.0 4.5 5.0
5.0 5.0 Navy SG Novacron .RTM. 2.5 5.0 4.5 5.0 4.5 5.0 5.0 Navy
CBN
[0099] For nearly all dyes, the crocking, lightfastness, ozone
resistance, burnt gas fading, and 120.degree. F. and 160.degree. F.
washfastness results were outstanding. Results were significantly
better than those achieved with reactive dyeing of cotton at
comparable color levels on a continuous dye range. Table 2C below
details the differences in performance for different types of dyed
fabrics and the polymer-dye matrix substrates described herein.
*After wash swatch is darker than the original swatch with no color
loss
TABLE-US-00007 TABLE 2C Performance Comparison of Ring Dyed Fabrics
Crocking Lightfastness AATCC 8 AATCC 16E Description Dry Wet 20 hrs
Dark Indigo Denim 3.0 1.0 3.0 Dark Sulfur Denim 4.0 1.5 3.0 Dark
Pigment Piece dye 3.5 1.5 4.5 Medium Stonewashed Indigo Denim 4.0
2.5 2.5 Dark Chambray indigo 4.0 2.0 3.0 Bleached Indigo Chambray
4.0 3.0 2.0 Polymer-Dye Matrix (Indigo color) 5.0 4.0 4.0
Polymer-Dye Matrix (Most Colors) 4.5-5.0 4.0-4.5 3.5-4.5
Example 2B
Ring Dyeing--Verification of Ring Dyed Effect
[0100] Fabric from Example 2A was folded over the edge of a table
and the folded area lightly sanded with 100 grit sand paper to
remove the surface coating of the polymer/dye film on the surface
of the fabric. In all cases, white yarn was detected in areas where
the fabric was sanded demonstrating that the fabric was ring
dyed.
Example 3A
Treatment of 9.5/1 Ansler Ring Spun 100% Cotton Yarn to Create
Denim-Like Ring Dyed Fabric (Sample ID 198-10 and 198-11)
[0101] A mixture was prepared by mixing 75.0 grams of TST U-60 (60%
active urethane) (Texstream Technologies), 1.0 gram of Defoamer CH2
(Apollo Chemical Company), 15.0 grams of NOVACRON.RTM. Navy CBN
(available from Huntsman Corporation), and 0.75 grams of
NOVACRON.RTM. Red SB (available from Huntsman Corporation). The
mixture was diluted to one liter with 110.degree. F. water. A
single end 9.5/1 Ansler Ring Spun 100% cotton yarn was dipped in
this mixture and excess mix removed with a rubber over metal
squeeze roller achieving a wet pickup of 130%. The yarn was dried
by blowing hot air (86.degree. C.) onto the yarn for a period of
105 seconds. The processed yarn was woven as the filling yarn
across 32 ends/inch of 4.5/1 open end 100% cotton yarn. A reverse
oxford weave inserting 56 picks per inch of the 8.5/1 treated yarn
produced a canvas-like fabric with yarns in one direction that were
dyed.
[0102] An additional Red/Orange color was produced from the same
yarn by using 10.0 g/l of NOVACRON.RTM. Red SB and 2.0 g/l of
NOVACRON.RTM. Orange C-3R (available from Huntsman Corporation)
using the same formulation and process described above.
[0103] The fabric was cut into 12 inch strips and processed through
a continuous oven at 340.degree. F. for 70 seconds to ensure that
the coating was totally cured. The dye was immobilized by the
application of alkali and salt brine followed by steaming as
described in Example #1B.
Example 3B
Treatment of 80/15/5 PROTEX.RTM. C/Pima Cotton/KEVLAR.RTM. Flame
Resistant Yarn to Create Lightweight Denim-Like Flame Resistant
Ring Dyed Twill Fabric
[0104] A mixture was prepared by mixing 75 grams of TST U-60 (60%
active urethane), 1.0 gram of defoamer CH2, 15.0 grams of
NOVACRON.RTM. Navy CBN, and 0.75 grams of NOVACRON.RTM. Red SB in
one liter of 110.degree. F. water. A single end of 80/15/5
PROTEX.RTM. C (modacrylic fiber)/Pima Cotton/KEVLAR.RTM.
(para-amid) flame resistant yarn was dipped through this mixture
and excess mix removed with a rubber over metal squeeze roller to
achieve a wet pickup of 130%. The yarn was dried by blowing hot air
(86.degree. C.) onto the yarn for a period of 105 seconds. The
processed yarn was woven as the filling yarn across 96 ends/inch of
36/1 Ring Spun yarn comprised of 65/25/10 FR
Rayon/KEVLAR.RTM./Nylon (polyamide) fiber mixture. A 2.times.1 Left
Hand twill fabric was produced by inserting 58 picks per inch of
the dyed/treated yarn.
[0105] An additional Red/Orange color was produced from the same
yarn by using 10 g/l of NOVACRON.RTM. Red SB and 2.0 g/l of
NOVACRON.RTM. Orange C-3R using the same formulation and process
described above.
[0106] The fabric was cut into 12 inch strips and processed through
a continuous oven at 340.degree. F. for 70 seconds to ensure that
the coating was totally cured. The dye was immobilized by the
application of alkali and salt brine followed by steaming as
described in Example #1B.
Example 3C
Treatment of 15.1/1 50/50 Cotton/Polyester Core-Spun Polyester Yarn
to Create Lightweight Denim-Like Ring Dyed Twill Fabric (Sample ID
198-9)
[0107] A navy mixture was prepared as described in Example 1C. A
single end of 15.1/1 50/50 cotton/polyester core-spun yarn with a
polyester core was dipped through this mixture and excess mix
removed with a rubber over metal squeeze roller achieving a wet
pickup of 130%. The yarn was dried by blowing hot air (86.degree.
C.) onto the yarn for a period of 105 seconds. The processed yarn
was woven as the filling yarn across 84 ends/inch of 60/40
cotton/polyester warp yarn. A 2.times.1 Left Hand twill fabric was
produced by inserting 58 picks per inch of the dyed/treated
yarn.
[0108] The fabric was cut into 12 inch strips and processed through
a continuous oven at 340.degree. F. for 70 seconds to ensure that
the coating was totally cured. The dye was immobilized by the
application of alkali and salt brine followed by steaming as
described in Example #1B.
Example 3D
Removal of Size and Finishing of the Treated and Dyed Yarn
[0109] Before finishing, sizing from the warp yarns was removed and
the fabrics from Examples 3A, 3B, and 3C scoured and bleached. The
desize/bleach formulation consisted of hydrogen peroxide, an
organic stabilizer, sodium hydroxide, a non-ionic surfactant, and a
chelating agent. This mixture was padded onto the fabric at
120.degree. F. with a wet pickup of 150%, rolled on a tube, wrapped
in plastic, and placed in a warm 105.degree. F. oven for 12 hours.
Fabric was washed and dried. Little to no dye was removed in the
desize/bleaching process. The fabric was finished with
PHOTOBEX.RTM. JVA as described in Example #1C, made into pant legs,
and laundered as described in Example #1D. Pant legs of Example #3A
(Denim) were laundered for 90 minutes instead of 60 minutes before
rinsing. The pant legs clearly demonstrated that the dyed yarn was
ring dyed and that the portions that were abraded had the white
bleached color of the yarn showing through. All fabrics were tested
after finishing assessing colorfastness performance. Results are
provided in Tables 3A-3B below.
TABLE-US-00008 TABLE 3A Treatment of Yarn with Urethane and Dye
Sample Yarn Fiber Warp Ends/ Picks/ ID Size Description Blend Color
Yarn Fiber Blend inch Inch Weave 198-9 18/1 RS 50/50 Indigo 15.5/1
60/40 84 55 2 .times. 1 LH Prospin cotton/ RS Cotton/Polyester
Twill polyester 198-10 8.5/1 RS Ansler 100% Indigo 4.5/1 100%
Cotton 32 45 Reverse Cotton OE Oxf. 198-11 8.5/1 RS Ansler 100%
Red/ 4.5/1 100% Cotton 32 45 Reverse Cotton Org OE Oxf.
TABLE-US-00009 TABLE 3B Performance of Woven Fabrics AATCC AATCC
16A 8 Lightfastness AATCC 61 3A Sample Crocking 20 40 Washfastness
ID Color Dry Wet hrs hrs Shade .DELTA. Actetate Cotton Nylon
Polyester Orlon Wool 198-9 Indigo 4.0 3.5 4.0 3.5 4.0 4.5 4.0 4.5
4.5 5.0 5.0 198-10 Indigo 4.0 3.5 4.5 3.5 4.0 4.5 4.0 4.5 4.5 5.0
5.0 198-11 Red/ 4.0 3.5 4.0 3.5 4.0 4.5 3.5 4.5 4.5 5.0 5.0 Org
[0110] In all cases, colorfastness performance for all fabrics was
good. The measurement of rub fastness for the depth of colors being
evaluated was exceptional with little to no color transferred in
either dry or wet form. Minimal staining of untreated yarns was
observed in any woven fabrics nor staining on multi-fiber swatches
even at elevated 160.degree. F. wash temperatures.
[0111] For the flame resistant fabric produced from Example #3B,
vertical flammability testing when tested in accordance to ASTM D
6413 initially and after 100 washing and drying cycles had char
lengths under 4 inches and after flame less than 2 seconds. The
polymer/dye coating was found to have no effect on the flammability
performance.
Example 4
Impact of Urethane/Dye Ratio on Color, Durability, Colorfastness
Performance of 100% Cotton
[0112] An 8.7 oz/yd2 3.times.1 right hand twill constructed from
30.25/2 combed ring spun 100% cotton warp yarn and 25.25/2 combed
ring spun 100 cotton filling yarn with 117 ends per inch and 56
picks per inch was treated with a mixture of 10.0 g/l of
NOVACRON.RTM. Navy CBN and 69 g/l, 46 g/l, and 23 g/l of TST-U60
urethane. Wet pickup of the urethane/dye mixtures was 72%. All
urethane and dye migrated to the yarn surface upon drying and
curing at 340.degree. F. for 105 seconds. Dye/urethane solids
ratios were varied from roughly 1.3:1 to 4:1 and colorfastness
performance was evaluated after fixation of the dye with
alkali/salt as outlined in Example #1B. Higher urethane to dye
ratios yielded better colorfastness performance. Testing results
are detailed in Table 4.
TABLE-US-00010 TABLE 4 Colorfastness Performance as a Function of
Urethane:Dye Ratio Test Method AATCC AATCC Percent Solids on AATCC
16A AATCC 23 Fabric 8 Lightfastness 109 Gas Navy Urethane:Dye
Crocking 20 40 Ozone Fade Urethane CBN Ratio Dry Wet hrs hrs 2
cycles 1 Cycle 3.00 0.75 4.0:1 5.0 4.0 4.5 4.0 4.5 4.5 2.00 0.75
2.6:1 5.0 4.0 4.5 4.0 4.5 4.5 1.00 0.75 1.3:1 5.0 4.0 4.0 3.5 4.0
4.5 Percent Solids Test Method on Fabric Urethane: AATCC 61 3A Navy
Dye Washfastness (160.degree. F.) Urethane CBN Ratio Shade .DELTA.
Acetate Cotton Nylon Polyester Orlon Wool 3.00 0.75 4.0:1 4.5 5.0
5.0 5.0 5.0 5.0 5.0 2.00 0.75 2.6:1 3.5 4.5 5.0 5.0 5.0 5.0 5.0
1.00 0.75 1.3:1 2.0 5.0 5.0 5.0 5.0 5.0 5.0
Example 5
Two Tone Dyeing of 100% Cotton Fabric and Yarn--Ring Dyeing Process
Followed by Piece Dyeing Process
[0113] A 12.1 oz/yd2 100% cotton canvas constructed from 4/1 open
end warp yarns and 8/2 open end filling yarns was desized, scoured,
and bleached in preparation for treatment.
[0114] Step 1--A mixture containing 4.1% urethane solids and 1.0%
NOVACRON.RTM. Blue CR was padded onto the fabric and excess
solution removed with squeeze rolls to achieve a pickup of 72%.
Fabric was dried, and the polymer cured by processing the fabric
through an oven set to 340.degree. F. The dye was fixed by
processing through a salt brine/alkaline solution followed by
steaming for 50 seconds at 218.degree. F. No appreciable dye was
removed in the washing process and a medium blue color
resulted.
[0115] Step 2--a reactive dye mixture comprised of 4.0% alginate
antimigrant, 4.7% salt brine solution, 0.1% barasol wetting agent,
and 0.5% NOVACRON.RTM. Yellow CR01 was padded onto the fabric,
excess solution removed with a squeeze roll to a wet pickup of 75%,
the fabric dried with a combination of electric predryers and steam
cans. The reactive dye was fixed by processing through salt
brine/alkaline solution as described in Example 1C, washed,
neutralized with acetic acid, and dried.
[0116] The blue shade was greener in cast than before treatment.
The surface of the fabric was sanded revealing the dyed yellow
fiber beneath the blue-green polymer matrix.
Example 5A
Two Tone Dyeing of 100% Cotton Fabric and Yarn--Piece Dyeing
Process Followed by Ring Dyeing Process
[0117] The same fabric from Example 5 was selected. Step 2 from
Example 5 was followed to dye the ground color. The dyed fabric was
treated with the process described in Example 5, step 1 in which
the fabric was ring dyed with a Blue color. Compared to the fabric
color from Example 5, step 1 prior to step 2, the fabric color was
greener. When the surfaced was sanded, the yellow base color was
readily apparent with almost so staining from the blue in the
yellow ground color. When wet processed with pumice stones, tonal
effects were created ranging from dark blue-green to light yellow
green coloration.
Example 5B
Treatment of 100% Polypropylene
[0118] A 4.0 oz/yd2 100% polypropylene fabric constructed from 625
denier polypropylene woven with 24 ends and picks into a plain
weave was processed as described in Example 5 , step 1 except the
polymer was cured by placing in a dispatch oven at 235.degree. F.
for 10 minutes. The fabric after the initial dyeing process was
blue; however, after processing as described in Example 5, step 2
with the yellow reactive dye, the cast of the fabric did not
appreciably change and remained blue. When sanded removing the
surface polymeric/dye matrix, the white polypropylene was readily
apparent. None of the yellow reactive dye was fixed to the
polypropylene.
Example 6
Treatment of 88/12 Cotton/Nylon Flame Resistant Fabric
[0119] A 5.5 oz/yd2 woven fabric consisting of a 18/1 75/25
cotton/nylon 66 warp and a 16/1 100% cotton filling with a
construction of 108.times.50 in a 3.times.1 left hand twill weave
was desized, scoured, and bleached. The fabric was treated with a
urea precondensate of tetra-kis hydroxy methyl phosphonium chloride
and cured with gaseous ammonia to produce a flame resistant fabric
with 2.4% phosphorus content. The treated substrate was padded
through a mixture containing 69 g/l TST U-60 (4.14% urethane
solids) (Texstream Technologies), 0.1% Defoamer CH2 (Apollo
Chemical Company), 15 g/l NOVACRON.RTM. Navy CBN (Huntsman
Corporation--Reactive Black 5). A wet pickup of 72% yielded a
urethane concentration of 3.0% solids and dye solids add on of
1.34%. Fabric was processed through predryers to reduce the water
content to about 60% and completely dried on steam cans. Curing was
completed by heating to 340.degree. F. for a period of 65 seconds.
The dye was fixed by padding and steaming an alkali/salt mixture as
described in Example 1C.
[0120] Fabric was washed, dried, and tested for crocking,
lightfastness, and washfastness at 160.degree. F. Vertical
flammability was tested on treated undyed fabric, treated unwashed
dyed fabric, and dyed fabric after a one hour stonewash procedure.
(Stonewashing was done in a 65 lb Washex with liquor to fabric
ratio of 12:1 and a pumice stone to fabric ratio of 2:1 at a
temperature of 130.degree. F.). Colorfastness results were
excellent and vertical flammability testing passed with char
lengths less than 4.0 inches when tested in accordance with NFPA
701 protocol. Lightfastness results were a function of dye
selected. Three other reactive dyes were evaluated and results have
been depicted in Table 5.
TABLE-US-00011 TABLE 5 Colorfastness Performance as a Function of
Urethane:Dye Ratio Test Method % Solids AATCC 8 AATCC 16A on Fabric
Crocking Lightfastness Washfastness (160.degree. F.) Urethane Dye
Dye Dry Wet 20 hrs Shade .DELTA. Acetate Cotton Nylon Polyester
Orlon Wool 3.00 1.00 Reax 5.0 3.0 1.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Black 5 3.00 1.00 Reax 5.0 3.5 2.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Blue
261 3.00 1.00 R Yel 5.0 4.5 3.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 174
NFPA 701-Vertical Flammability (inches) % Solids Initial 60 min on
Fabric White Initial-Dyed Stonewash Urethane Dye Dye Warp Warp Fill
Warp Fill 3.00 1.00 Reax 3.94 3.75 3.75 3.50 3.50 Black 5 3.00 1.00
R Blue 261 3.00 1.00 R Yel 174
[0121] 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.
[0122] 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.
[0123] 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.
* * * * *