[0001] This invention relates to a process for generating patterns exhibiting high visual
contrast on textile substrates, and novel products which may be produced thereby.
More specifically, one embodiment of this invention relates to a process wherein individual
constituent fibers in an area on the surface of a textile substrate defining a pattern
are thermally conditioned or treated to permit relatively rapid extraction of dye
from those fibers by a solvent, while adjacent fibers which have not been so thermally
conditioned or treated resist such rapid dye extraction, thereby resulting in fabrics
wherein, following the controlled exposure to a suitable solvent, the heat-treated
pattern areas contain visually less dye than adjacent, solvent exposed pattern-complementary
areas.
[0002] Processes for generating patterns on the surface of textile substrates are well known
in the art. Such processes may or may not require the pattern-wise application of
dye to achieve a pattern, or even a dye-defined pattern, on the substrate surface.
Among those processes which do not require the pattern-wise application of dye are
included processes wherein heat, for example, from a heated embossing roll or in the
form of impinging heated fluid streams, is directed onto the substrate surface in
a pattern configuration prior to a dyeing step. The thermally treated portions of
the surface accept dye to a different (generally greater) degree than do the untreated
portions, thereby usually resulting in pattern areas having higher, visually contrasting
aye concentrations. Other processes rely on a variety of physical effects to define
or establish patterned areas on the substrate surface. For example, some processes
rely on physical compression and perhaps heat setting of individual fibers to imprint
the surface and thereby define a pattern. Other systems may rely on fiber entanglement
to yield visually distinct areas on the substrate surface.
[0003] A process disclosed in our copending Application, published as GB 2 065 035 A,
relies upon streams of heated fluid, which are made to -impinge upon the substrate
surface in a pattern configuration, to selectively shrink, melt, or otherwise thermally
deform or distort individual yarns or portions of individual yarns comprising the
substrate surface, thereby producing visually distinct areas on the substrate surface
in those areas containing yarns exposed to the heated fluid streams.
[0004] This technique can produce patterns which are quite detailed and which, under some
circumstances, can achieve rather high levels of visual contrast between pattern and
pattern-complementary (i.e., background) areas, even though not requiring the pattern-wise
application of dye. This is particularly true if the substrate is, for example, a
pile fabric and the pile yarns have been heated sufficiently to induce substantial
thermally-induced longitudinal shrinkage among the individual pile yarns. The resulting
sculptured or surface contoured effect can result in dramatic contrast levels between
pattern and pattern-complementary areas, provided the surface is appropriately illuminated.
However, the degree of contrast is often heavily dependent upon the type and direction
of the incident illumination. When non-pile textile substrates are patterned using
this technique, the individual fibers are softened and may undergo some shrinking
or melting; contrast, however, is frequently limited even under optimum illumination
with such fabrics. Using a dye which is selectively applied in pattern areas only
can impose formidable constraints if fine detail, or strict reproduceability, as production
speed, and inventory flexability, is desired. Colors must be carefully matched, dye
runs coordinated and scheduled, and, of course, the dye must be applied with great
precision and accuracy. These constraints have been formidable.
[0005] It is therefore desired to have available an economical, commercially practical process
wherein patterning may be achieved -using the pattern-wise application of heat or
other conditioning agent, rather than the pattern-wise application of dye, to individual
yarns on the substrate surface, and wherein the degree of visual contrast between
pattern and pattern-complementary areas on the substrate surface may be controllably
varied from relatively low to relatively high values, ano wherein the perceived contrast
is not significantly dependent upon the nature of the illumination. The process of
this invention involves the treating or conditioning, by physical or other means,
of individual yarns in the pattern areas of the substrate to permit the subsequent
selective extraction of dye in treated yarns processed in a controlled solvent-based
extraction step, which extraction step has substantially no visible effect on adjacent,
untreated yarns forming the pattern-complementary areas of the substrate. The dye
may be applied to the yarns either prior to or following the treating or conditioning
step. The role played by the treating or conditioning agent in this invention may
be thought of as being somewhat similar to that of a catalyst, in the sense that the
chosen solvent extracts dye with much greater speed from the treated yarns than from
the untreated yarns. Generally speaking, the chosen solvents useful in the practice
of this invention will, given sufficient exposure, extract dye from untreated areas
as well as treated areas, and perhaps to the same extent, but will not do so at the
same rate.
[0006] Figure 1 depicts a pile fabric, comprised of thermoplastic and non-thermoplastic
yarns, in which heat conditioning has caused thermal deformation, in the form of longitudinal
shrinkage, to individual thermoplastic pile yarns; dye has then been selectively extracted
from those thermally deformed fibers.
[0007] Figure 2 depicts a pile fabric in which heat conditioning has caused thermal deformation,
in the form of longitudinal shrinkage, to tufts or groups of thermoplastic pile yarns;
dye has then been selectively extracted from those thermally deformed yarn groups.
[0008] Figure 3 depicts a flat knitted fabric comprised of thermoplastic yarns wherein heat
conditioning has caused thermal deformation, in the form of melting and/or fusing
of individual yarns; dye is selectively extracted from the deformed region of the
fabric.
[0009] Figure 4 depicts a textile substrate in which dye has been selectively extracted
from the heat-treated diamond-shaped areas, in accordance with the teachings of this
invention.
[0010] In one preferred embodiment of the invention, a textile fabric comprised of polyester
(e.g., polyethylene teraphthalate) yarns which have been conventionally dyed with
a disperse dye is impinged with heated streams of fluid, for example, air, in a pattern-wise
configuration by an apparatus similar to that disclosed in commonly assigned U. S.
Patent Application Serial Number 253,135, referenced above. This apparatus is discussed
herein as merely one example of an apparatus which may be used to practice this invention;
commonly assigned U. S. Patent No. 4,364,156, also incorporated by reference herein,
further defines a manifold which may prove advantageous when used in conjunction with
the apparatus of U. S. Patent Application Serial No. 253,135. It is believed any means
by which appropriate amounts of heat may be suitably applied in a pattern-wise configuration
to the yarns comprising the surface of the textile substrate to be patterned may be
employed. For example, a laser beam of suitable power and intensity, directed onto
or over the substrate surface in a pattern configuration, may be used instead of heated
air streams.
[0011] It is theorized that, where thermal energy is used to condition the yarns, the heat
tends to induce a decrease in the internal orientation of at least portions of individual,
untensioned yarns in those pattern areas where the maximum rate of solvent extraction
of dye is desired. The decrease in orientation is thought to promote the entry of
the solvent into the yarn interior, perhaps by generating voids between adjacent constituent
molecules, and thereby accellerate the dye extraction process. It is also theorized
that thermal conditioning may tend to cause radial migration of dye molecules from
the yarn interior toward the yarn surface which, contributes to the observed accellerated
rate of dye extraction by the solvent in thermally treated yarns. Generally speaking,
thermal conditioning of thermoplastic yarns is accompanied by thermal deformation
or distortion of the yarns, e.g., softening, longitudinal shrinking, melting, or fusing
of individual yarns. These effects are schematically depicted on various substrates
in Figures 1 through 3. It is believed maximum rates of selective dye extraction in
accordance with the teachings of this invention may be expected from those thermoplastic
yarns or portions of yarns which exhibit such thermally induced deformations, as compared
with thermoplastic yarns in which no thermal deformation is observed. However, such
softening, shrinking, melting, or fusing, or other readily observable, external effects
are not believed to be necessary to the practice of this invention. The degree to
which such observable effects occur depends upon many factors, such as the type and
composition of yarn used, the degree to which the individual yarns are free to shrink,
the nature of the applied heat, etc.
[0012] It is also believed that conditioned polymeric yarns have increased voids between
adjacent polymer molecules within the fibers comprising the yarns, as compared to
unconditioned yarns of the same type, thereby enhancing the migration rate of solvent
molecules into and out of the yarns.
[0013] The following table was prepared to quantify the effects of thermal conditioning
on one example of a polyester yarn, using a preferred suitable solvent. A package
of yarn, 20/2 T-811W Bright DACRON (DACRON is a trademark of DuPont), manufactured
by Milliken & Company from DuPont polyethylene terephthalate fiber, was dyed in a
laboratory package dye machine using Eastman Polyester Blue GLF (Color Index Name
Disperse Blue 27). Lengths of this yarn were heat treated by immersion for 5 seconds
in a fluidized bed, Model SBS-2 distributed by Fisher Scientific Company of Pittsburg,
Pennsylvania, over a range from 300°F. to 500°F., in increments of 25°F. Measurements
of length before and after heat treatment allowed calculation of the percent shrinkage
at each temperature. Standard lengths were then solvent extracted by immersing them
in 5 ml of methylene chloride at room temperature for one minute and then removing
the yarn from the solvent. The UV-Visible spectra of these extracts were then recorded
to yield the absorbence attributed to the blue dye at a wavelength of between 592
and 595 millimicrons, thereby giving an indication of the amount of dye extract by
the solvent.
[0014] The results are tabulated below:

[0015] It can be seen from this table that, for this particular yarn/solvent system, the
rate of dye extraction generally increases after brief thermal conditioning at temperatures
above about 300
0F., and increases dramatically after brief thermal conditioning at temperatures extending
from about 425°F. to somewhere between about 475°F. and 500°F., i.e., a temperature
just below the melting point of the unconstrained yarn. Where the yarn is constrained,
somewhat higher temperatures, i.e., 500°F. or above, may be employed to generate increased
shrinkage and increased dye extraction rates.
[0016] After the fabric has been suitably heat treated in the desired pattern configuration,
the fabric is then exposed for a controlled period of time to a solvent which, during
that time period, selectively extracts dye from the heat treated areas only, and which
has relatively little or substantially no effect upon those portions of the fabric
surface which have not been heat treated in accordance with the teachings of this
invention. There is no requirement that the heat treated fabric be immediately exposed
to the solvent, or be stored under any particular set of conditions following the
pattern-wise heat treatment of the fabric. There is also no requirement that the fabric
be dyed prior to the pattern-wise application of heat; good results may be obtained
if a fabric is first subjected to the pattern-wise application of heat, then piece
dyed, then exposed to a solvent, all in separate independent steps, in accordance
with the teachings of this application. Because under such conditions the heat treated
areas tend to pick up more dye than the untreated areas, extraction times may be extended,
because more dye may be required to be extracted..
[0017] Any suitable solvent may be used. Solvents which have been used with fabrics containing
polyester yarns which were dyed using disperse dyes include hot perchloroethylene
and 1,1,1-trichtoroethane. Other solvents which may be found to be satisfactory may
be found in Table II of the technical article "Interactions of Nonaqueous Solvents
with Textile Fibers - Part I: Effects of Solvents on the Mechanical Properties of
a Polyester Yarn" by A. S. Ribnick, H.-D. Weigmann, and L. Rebenbeld, appearing in
the Textile Research Journal, December 1972, at pages 720-726 (Table II at page 722)
as well as in Table I of the technical article "Interactions of Nonaqueous Solvents
with Textile Fibers - Part II: Application of the Solubility Parameter Concept to
Polyester Fiber-Solvent Interactions" by B. H. Knox, H.-D. Weigmann, and M. G. Scott,
appearing in the Textile Research Journal, March, 1975 at pages 203-217 (Table I at
206); the contents of these two tables are hereby expressly incorporated by reference.
[0018] A preferred solvent for polyester yarn/disperse dye combinations is methylene chloride,
which may be used at room temperature and which is capable of extracting substantial
quantities of disperse dye from pattern-wise heat treated polyester relatively quickly.
In one embodiment, polyester-containing fabric which has been heat treated in a pattern-wise
configuration may be immersed in a bath of methylene chloride at room temperature
and agitated for a short period of time to assure proper circulation of the solvent
in the vicinity of the yarns comprising the patterned areas of the fabric. The methylene
chloride solvent can, in a matter of 30 to 60 seconds or less, extract substantially
all the visible dye from those pattern areas of the fabric which have been heavily
heat treated. During the same time period, the solvent will extract visably less dye
from pattern areas, or portirons of individual yarns, which have been less heavily
treated, i.e., exposed to lower temperatures, and will extract substantially no dye
from those areas or yarns, or portions of yarns, which have not been heat treated.
Using warm or hot methylene chloride solvent produces the same selective extraction
effects, but within a substantially shortened time period virtually complete dye extraction
may be achieved in heavily patterned areas in a matter of a few seconds. It must be
remembered that if solvent exposure time is not monitored carefully, complete dye
extraction will occur in lightly treated or non-treated areas as well.
[0019] Means other than immersion may be used to bring the fabric into contact with the
solvent if desired, e.g., the solvent may be sprayed on the fabric. It is also contemplated
that, following application of the solvent, physical agitation of the yarns, to wash
dye saturated solvent from the surface may be used to facilitate the extraction process.
Means for halting solvent action may vary. Most simpley, of course, the solvent may
be washed or otherwise removed from the substrate surface after the desired "residence
time" or exposure time has passed.
[0020] It is preferred that the chosen solvent be one which is not readily flammable, and
of course should be one which is neither grossly toxic to humans nor destructive to
the yarns used. It is believed that suitable solvents should be selected from those
solvents having a hildebrand solubility parameter ( ) which is appropriate to the
yarn of interest. It has been found, for example, that for yarns consisting essentially
of polyethylene teraphthalate ( 10.7), workable solvents should have hildebrand solubility
parameter values within the range of about 8 to about 14. Solvents having values closest
to 10.7 do not necessarily result in maximum dye extraction rates and are not necessarily
preferred over other solvents having more extreme values. Factors such as the size
and therefore the accessibility of the solvent molecule relative to the voids between
the polymer chains within the fibers which make up the yarn must be accommodated.
High solvent migration rates are desirable. Solvents having values substantially higher
or lower than 10.7 may interact quite well with different portions of the polyethylene
teraphthalate molecule and produce high dye extraction rates. It has been found that
suitable solvents having solubility parameter values between about 9 and about 10,
and also between about.11.5 to about 13, often work quite well; suitable solvents
from the former group tend to interact well with the aromatic portion of the polyethylene
teraphthalate molecule, while solvents from the latter group tend to interact well
with the aliphatic portion of that molecule.
[0021] The following Examples are intended to describe particular applications of the invention,
and are not intended to be limiting. The device used to pattern the fabric with streams
of heated or hot air was similar to those devices disclosed in commonly assigned U.
S. Patent Application Serial No. 253,135 and U. S. Patent No. 4,364,156, referenced
and made a part of this disclosure hereinabove.
Example 1
[0022] A 100% polyester napped pile fabric having a weight of 10 oz. per square yard, identified
by Milliken & Company as Style 8301, was conventionally dyed with disperse dyes to
give a uniform medium brown color. The fabric was then treated with streams of hot
air from the heated air device described hereinabove to generate a sculptured pile
fabric having a pin dot array of depressed, thermally shrunken yarns. The fabric speed
in the device was 6.5 ypm; the manifold air temperature was about 670°F. The coloration
in the sculptured prior to exposure to the solvent areas was slightly darker than
in the background area, where the pile remained substantially erect. The patterned
fabric was immersed in a bath of methylene chloride at 23°C. for one minute, removed,
and dried in a stream of room temperature air. When completely dry the fabric exhibited
a pattern of very light brown sculptured dots on a background substantially unchanged
in color. The contrast exhibited by the pattern areas on the treated sample was excellent,
and the pattern was very easy to see from any angle.
Example 2
[0023] A 44 gauge double needle bar raschel knit polyester pile fabric, identified by Milliken
& Company as Style 6590 having a weight of approximately 9 oz./yd.
2 was dyed with a disperse dye to give a uniform deep blue color. This fabric was treated
with streams of hot air using the device disclosed above to yield a dot array of thermally
shrunken pile. The fabric speed in the device was 25 ypm; the manifold air temperature
was about 820°F. When treated with methylene chloride as described above for 1 minute,
removed and air dried, the final product exhibited a uniformly deep blue field with
a substantially white pin dot array, corresponding exactly to the shrunken pile areas,
superimposed thereon.
Example 3
[0024] A raschel knit pile fabric of 100% polyester, identified by Milliken & Company as
Style 180 having a weight of approximately 5 oz./yd.
2 was dyed to a uniform green color with disperse dye. The fabric was treated with
streams of hot air in pattern configuration using the above-referenced device. The
fabric speed in the device was 7 ypm; the manifold air temperature was about 700°F.
A sculptured image was obtained which was difficult to read at all angles of light.
The fabric was then dipped in methylene chloride at 23°C. for 30 seconds, removed
and dried with a stream of cool air to yield a highly contrasting design of white
against a green background that was much more readable than the untreated patterned
fabric.
Example 4
[0025] A 100% polyester knit fabric (interlock) manufactured by Milliken & Company and identified
as Style 2651 having a weight of 3.0 oz.yd.
2 was eyed to a deep blue shade using disperse dye and imaged by computer controlled
streams of heated air using the above-referenced device. The fabric speed in the device
was 3.75 ypm; the manifold air temperature was about 820°F. Prior to exposure to the
solvent, the image was darker in the heated area. When dipped in methylene chloride
at 23°C. for 30 seconds and air dried, the imaged area became lighter. A second portion
of the same fabric, similarly patterned and exposed to methylene chloride for 60 seconds,
exhibited contrast which was even greater, with the color of the unimaged area remaining
constant.
Example 5
[0026] A woven fabric containing an intimate blend of polyester and cotton in the ratio
65/35 manufactured by Milliken & Company and identified as Style 2602, weighing approximately
4.75 oz./yd. was union dyed to a navy blue shade. The fabric was imaged with hot air
streams to yield a diamond pattern with flowers in the center, using the above-referenced
device. The fabric speed in the device was 6 ypm; the manifold air temperature was
about 700°F. On the dark navy fabric, there was only slight contrast between the imaged
and the unimaged areas. After dipping in methylene chloride at 23°C. for 1 minute,
the dye was extracted from the polyester yarns that had been thermally tranformed
by the hot air while the dye in the cotton fibers remained unaffected. The result
was a light blue pattern on a darker navy background due to extraction of the dye
within the polyester fibers.
Example 6
[0027] A napped woven fabric containing a disperse-dyeable polyester yarn in the filling
direction and a cationic-dyeable polyester yarn in the warp direction was woven in
such a way that, after cross-dyeing, napping created a sculptured effect consisting
of square-shaped non-pile areas, approximately 0.1 inches per side, which appeared
black (cationic dye) in a field of grey (dispersed dyed nap). The fabric was manufactured
by Milliken & Company and identified as Style 8317 having a weight of approximately
10 oz./yd.
2. The fabric was imaged with a stream of hot air using the above-referenced device.
The fabric speed in the device was 6.75 ypm; the manifold air temperature was about
670°F. The fabric was immersed in methylene chloride at 23°C. for 1 minute, then dried.
The resulting pattern showed a highly contrasting white pattern area, and a black
pin dot on a grey background. The resulting effect was multicolor and showed good
contrast with the cationic dye removed to a much lesser extent, if at all, by the
solvent extraction process.
Example 7
[0028] A woven polyester fabric having both cationic-dyeable polyester yarn and disperse-dyeable
polyester yarn, identified as Style 8327 having a weight of 9.5 oz./yd.
2 was cross-dyed and then patterned with a stream of heated air at 760°F. in the above-referenced
device. Fabric speed was 6.75 ypm. The patterned fabric was then dipped in methylene
chloride for 1 minute at 23°C. After 1 minute the sample was removed and dried. It
showed strong contrast where the hot air had impinged, giving very light diagonal
blue line pattern against a field of medium-to-dark blue yarns.
Example 8
[0029] The fabric of Example 1 was similarly treated with hot air. The treated fabric was
then immersed for 5 seconds in a bath of methylene chloride heated to 35°C. The results
after removal from the solvent and drying were substantially identical to those achieved
in Example 1.
Example 9
[0030] The procedures of Example 1 were followed, except that acetone heated to 53°C. was
substituted for methylene chloride. The results were similar to those achieved in
Example 1.
Example 10
[0031] The procedures of Example 1 were followed, except that 1,1,1-trichtoroethane at 70°C.
was substituted for the methylene chloride. The results were similar to those achieved
in Example 1.
Example 11
[0032] The procedures of Example 1 were followed, except that perchloroethylene at 95°C.
was substituted for the methylene chloride, and the exposure time was extended to
5 minutes. The results were similar to those achieved in Example 1.
Example 12
[0033] The procedures of Example 1 were followed, except that ethanol at 73°C. was substituted
for the methylene chloride, and the exposure time was extended to 5 minutes. A very
slight change in the visual dye concentration was observed in the treated areas.
Example 13
[0034] The procedures of Example 1 were followed, except that the heat treatment with hot
air streams was done prior to conventional dyeing. The resulting fabric contained
dark brown dots on a medium brown field. Exposure of the patterned fabric to methylene
chloride for one minute at 23°C. results in a noticeable visual lightening of the
dot areas. Further exposure, for a total exposure time of 5 minutes, resulted in a
fabric exhibiting light beige dots on a medium brown field.
1. A method for patterning the surface of a textile substrate comprising thermoplastic
yarns, which comprises :
(a) selectively applying a treatment to pattern areas on said surface to enhance the
extractability of a dye from at least some thermoplastic yarns within said areas;
(b) exposing said surface to a solvent which extracts dye contained in said yarns
within the treated areas at a significantly faster rate than dye from untreated pattern-complementary
areas of said surface; and
(c) halting said solvent extraction after the desired degree of dye extraction in
said pattern and pattern-complementary areas has occurred.
2. A method according to claim 1, in which said treatment comprises decreasing the
relative internal orientation of treated yarns within said pattern areas.
3. A method according to claim 1 or 2. in which said treatment comprises the selective
application of heat.
4. A method according to claim 3, in which said heat is sufficient to induce thermal
deformation of yarns in said selected areas.
5. A method acording to claim 3 or 4, in which said heat is applied by directing streams
of heated fluid onto said substrate surface in pattern-wise configuration.
6. A method according to claim 3 or 4, in which said heat is applied by directing
a laser onto said substrate surface in pattern wise configuration.
7. A method according to any of claims 3 to 6, in which said yarns are dyed prior
to said treatment.
8. A method according to any of claims 3 to 6, in which said yarns are dyed following
said treatment but before said solvent extraction.
9. A method according to any preceding claim, in which said solvent is selected from
methylene chloride, perchloroethane and 1,1,1-trichloroethane.
10. A method according to any preceding claim, in which the dyed yarns comprise polyester
yarns, and said solvent selectively extracts a visually significant quantity of said
dye contained in the treatment polyester yarns in said pattern areas before a visually
significant quantity of dye is extracted from untreated pattern-complementary areas.
11. A method according to any preceding claim, in which the yarns comprise yarns of
polyethylene terephthalate dyed with a disperse dye.
12. A method according to claim 11, in which said dyed yarns in selected pattern areas
are heated to a temperature within the range of 163° to 260oC, and said solvent has a solubility parameter within the range of 8 to 14 hildebrands.
13. A patterned textile substrate, in which the pattern areas are comprised of polyester
yarns which are thermally deformed and said pattern-complementary areas are comprised
of polyester yarns which are substantially non-deformed and contain substantially
more disperse dye per unit yarn length than said deformed yarns.
14. A textile according to claim 13, in which said thermally deformed yarns comprise
yarns whereof at least a segment is longitudinally shrunken.
15. A textile according to claim 14, in which said thermally deformed yarns comprise
pile yarns whereof at least a portion near the tip is shrunken.
16. A textile according to claim 13 or 14, in which said shrunken segments or portions
of said deformed yarns contain less dye per unit length than unshrunken portions of
said yarns.
17. A textile according to claim 13, in which said thermally deformed yarns comprise
yarns whereof at least a portion of individual yarns is melted.
18. A textile substrate containing areas defined by polyester yarns which are visually
thermally deformed, and further containing areas defined by polyester yarns which
contain substantially no dye, said latter areas coinciding in substantially exact
registry with said former areas to define the pattern areas on said substrate surface.