Textile Research

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A Solvent-Dyeing Process for Aramid Fibers

J. Preston and W.L. Hofferbert, JR
Textile Research Journal 1979 49: 283
DOI: 10.1177/004051757904900506

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 283

A Solvent-Dyeing Process for Aramid Fibers

1
J. PRESTON AND W. L. HOFFERBERT, JR.
Monsanto Triangle Park Development Center, Inc., Research Triangle Park, North Carolina 27709, U. S. A.

ABSTRACT

A solvent-dyeing process for aramid fibers is described which is capable of producing fiber and fabrics having excellent
depth of shades. The brightness of the fibers and fabrics is quite high when the undyed fibers are bright. When properly
selected basic dyes are used, and when heavy shades are developed on the fabrics, good dyed lightfastness values are ob-
tained. Carpet samples of Nomex® dyed via the solvent-dyeing process described are considerably brighter, cleaner, and
deeper in shades than commercial carpet samples of Nomex dyed using the producer-recommended dyeing process. More-
over, the dyed lightfastness values (Gray Scale) are considerably higher for these solvent-dyed carpet samples. Thus.
ratings as poor as 2 and 1 after, respectively, 20 and 40 hours in the Fade-Ometer were obtained on the commercial
carpet samples, whereas certain of the test samples rated 2—3 even after 320 hours.
In addition to the improvement in dyeing obtained with the solvent-dyeing process, it was observed that the aramid
-phenyleneisophthalamide (MPD-I) and the polyisophthalamide of 4,4’-methylenedianiline
fibers based on poly-
m
(MDA-I) apparently undergo a certain degree of relaxation. For example, on blank dyeing in pyridine tenacity of the
the wet-spun MDA-I fiber decreased only slightly, while the initially somewhat low elongation-to-break value increased
significantly. For Nomex 10 dpf staple the average elongation-to-break value increased slightly, but the range of this
value narrowed considerably. Two rigid, rod-like, wholly aromatic fibers, the DuPont Company’s Kevlar® aramid
fiber, and the Monsanto Company’s experimental X-500 polyamide-hydrazide fiber, do not show the same type relaxation
effects exhibited by either MDA-I or MPD-I ( i.e. Nomex).Thus, the tenacity of the Kevlar increased somewhat, and
the initial modulus values for both rod-like fibers increased moderately.

Introduction undyed) fibers, which tend to develop a yellow to

’bronze color. In this paper a solvent-dyeing process
,
In recent y-ears aramid fibers have, ,gained
acceptance for aramid fibers is discussed which overcomes some of
in several end-use applications because of high heat the problems associated with previously published pro-
resistance and excellent resistance to burning accom- cedures for the dyeing and finishing of aramid fiber.
panied by low levels of smoke generation when these ,
, I .

fibers are forced to burn. Flame-resistant garments

have been introduced and have been accepted in critical Experimental .,
.

applications for use by firemen, foundry workers, race- °

Samples of 2~-ozj y-d2 (848 g ’m2) level-loop carpets,

car drivers, pilots of military aircraft, etc. Aramid
having Nomcx E-19 and MDA-1 as the face fibers and
fibers are often specified for applications where high
polypropylene as the primary backing, were prepared
inherent flame resistance (i.e., flame resistance ob- without latex backing. Specimens weighing 4 to 5 g
tained without use of additives) and low smoke genera- each were cut from the carpet samples and soaked over-
tion are criiical ’properties for furnishings, such as
night (16 h) ifi pyridine at room temperature prior to
carpets and drapes, which are used aboard military dyeing. The soaked specimens were allowed to drain
ships, in aircraft, and in hospitals, etc. , about one minute, then dropped into a 1% solution of
Although there are industrial applications. hott
(e ., dyestuff in py-ridine at the boil. The carpet specimens
gas nitration, leader cloths, laundry press nose covert were dyed for ~ h, removed from the dyebath, rinsed
electrical insulation, etc.) where the natural color fibers with hot running water for 30 min, and dried in an oven
are used, in general most of the applications for apparel, at 110°C. The following colors were developed on the
carpel and drapes require colored fibers. However, fibers from the dves cited: blue, Basacrvl Blue X3GL;
the aramid fibers are extremely difficult to dye to clean, red, Basacryl Red GL; yellow, Sevron Yellow 8GMF;
deep shades and are verv expensive to dye.’ More- orange, Astrazon Golden Yellow GL.
over, these fibers characteristically,show exceedingly A blank-dyed specimen of carpet also was prepared
poor dyed lightfastness, especially for the lighter shades, ’ which was in all respects, except for color, similar in
because of the severe discoloration of the natural (i.e. appearance to the dved specimens.
Yarn bundles were blank-dyed in pyridine (also in
1 Presented at the Symposium on "Recent Advances in Textile quinbline) prior to testin~ for single-filament tensile
Dyeing and Finishing," 176th Meeting of the ACS, Miami Beach,
Florida, September 10-15, 1978. properties.

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 284
-

Discussion and Results possibly because of more carboxylic end-groups in the

.

~
.

,
lower molecular weight (71inh 1.7-1.9)3 Nomex as
=

POLYMER STRUCTURES OF EIBERS USED. Aramid compared to MDA-I (’1inh 1.9-~.~).33

=

fibers may be obtained from structures such as the ,

.
polyisophthalamide of m-phenenediamine (MPD-I), PREVIOUS DYEING PROCEDURES FOR ARAMID FIBERS.
the polyisophthalamide 6f 4,4’-M’eth,%-Ienedianiline Several aqueous d eing procedures for aramid fibers
(MDA-1), and the polytrimellitimide-amide of 4,4’- ’have been publisher
particularly in the patent litera-
methylenedianiline (MDA-TM).2 ture. Because of the verv high. Tg values of aramid
fibers (> 250°C), most of ’these procedures relv on the
.

use ’of polar dyeing assists

such as phenols [10J,
chlorinated phenols_plus phenoy-ethanol E2], and mix-
tures of aromatic alcohols and aldehi-des [1 ] ; chlor-
inated aromatic hydrocarbtfns have also been reported
[7J as dyeing assists for mixed aliphatic-aromatic polv-
amides-e.g. nylon 6T. Use of aqueous solutions of
solvents for the polymer have been’taught [8, 10], but.
in our experience ~very poor fiber tensile, properties
result from using these conditions for dyeing. Dyeing
of dry-spun aramid fibers in the gel, state using a 20%
aqueous solution of solvent has been reported [13] to
.

give excellent dyeing, but it, is obvious frorn the tensile

data given, particularly the low, elongation-to-break
values, that the fibers were severely: damaged. -

Probably the most significant dyeing procedure puh-

The fibers employed in the dyeing experiments re- lished for aramid fibers is that recommended [5, 11]
ported here were MpD-I, as typified by DuPont’s com- by- the du Pont Company for the eyeing of Nomex. In
mercial fiber Nomex,’* and MDA-I, a fiber prepared this procedure acetophenone (alte,Q1’atively, ~Dymex,&dquo;
a product of Arkansas Company, Inc.). is used as the
in the laboratory by the Mo~isanto Textiles Company
and the sodium nitrate employed in the
for evaluation as an inherently name-resistant and, dye carrier,
low-smoke carpet fiber. Another fiber from the the surface of
aqueous dyebath apparently exhausts the~arrier onto
the fiber. The dye then exhausts into the
polyisophthalamide of 4,4’-isopropylidenedianiline (also carrier and migrates from the carrier into the fiber
known as bisaniline-A), BAA-I, was found to resist
during the course of the dyeing The chief
procedure.
discoloration by light rather well as the natural-colored drawbacks to this method of dyeing are: the use of
fiber, but it was not included in the dyeing studies pressure, long dyeing cycles, and-difficultn, in removing
the’carrier. (The somewhat poor dyed lightfastness
’

because of its solubility in the dyeing _solvent.

for fibers dyed by this procedure may be related to in-
complete removal of The tensile properties of carrie(.)
Nomex fibers after dyeing by this procedure have not
been reported but apparently are adequate. I

A solvent-dyeing procedure has been reported [6] in

,

the patent literature based on the use of glycols and

mixtures of glycols, ketones, and highly-polar solvents
for the MPD-I, such as dimethylsulfoxide, dimethyl-
No comonomers containing sulfonic acid are groups
formamide, and dimethylacetamide. Poor tensile prop-
required modify
to MPD-I or MDA-I to achieve good erties were obtained on Nomex and MDA7-1 fibers by
.
dyeability using the solvent-dyeing Ap- us on attempting to repeat the exatnples of this patent.
process. ,
parently, sufficient carboxylic acid end-groups are
available to’ achieve adequate dyeing with cationic SOLVENT-DYEING PROCESS FOR ARAMID FIBERS.
Prior to<the present work no suitable solvent-dyeing
dyes. The Nomex samples used in our studies dyed to
somewhat darker shades than the MDA-I samples, process for aramid fibers has been reported which pro- I

vides good depth of shade and clean shades on brightt

_ fibers, retains good fiber tensile properties, and gives
2
Although the latter structure is the basis for an aramid fiber adequate dyed lightfastness. Solven~ dyeing employ-
(Rh&ocirc;ne-Poulenc’s Kermel&reg;), it will not be discussed with here ing pyridine appears to provide all of the above to a
regard to the dyeing experiments; the structure is mentioned for
the sake of completeness with regard to aramids and because some
of the conclusions reached with regard to MPD-I and MDA-I 3
Determined at 30&deg;C on a 0.5% solution in dimethylacetamide
may also apply to MDA-TM. -

containing 5% dissolved lithium chloride.

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 285

suitable degree and may provide an

interesting lead for portant indeed, and the authors have observed that
further improvements in the dyed lightfa~tness of some cationic dyes that are highly stable on acrylic
aramid fibers. fibers show very .poor stability’ on aramid fibers.5 A
Although pyrid.ine has been included [10J in a list of list of dyes useful for Nomex is given Es, 11J in the.
useful dye assistants for the aqueous dyeing of aramid literature; the dves employed in this report (see Experi-
fibers, it apparently has not been used heretofore in mental) are of the type reported to be light-stable for
connection with solvent dyeing of these fibers. The Nomex. The results on light stability of undyed
mechanism by which the pyridine operates in the dyeing (natural) aramid fibers, commercially-dyed carpet
of the aramid fibers without adversely affecting tensile specimens from Nomex, and laboratory-produced and
. properties; particularly the elongation-to-break values, dyed carpet specimens from MDA-I are given below.
is ndt known. It has been reported [~~, however, that
pretreatment of nylon 66 fibers with pyridine followed LIGIiT STABILITY OF NATURAL ARAMID FIBERS. It is
by washing and drying is useful in &dquo;opening up&dquo; the well known that the light stability of aramid fibers is
structures of these fibers before aqueous dyeing by con- rather poor. In addition to a loss in tensile properties,
ventional procedures. ,
particularly elongation-to-break, upon exposure to light,
All of the dyes employed in the present work are a pronounced color buildup is noted. For MPD-I (t.g.
soluble in pyridine, and dyeing proceeds very rapidly. ~omex) bronze
a color quickly develops, probably as a
But to achieve level dyeing, about two hours dyeing result of a photo Fries rearrangement E3] under oxygen-.
,time at the boil was required, and very deep shades free conditions and an oxidative degradation in the
were developed. To obtain level dyeing for lighter presence of air E4]. The extent of the discoloration of
’shades, the fiber can be presoaked in pyridine, and the the fiber can be detected by the, poor Gray Scale
dyeing time (and temperature) can be reduced to pro- Ratings (Table I). For unstabilized MDA-I an .even
duce the desired effect. more intense color develops (Table I ), probably as a
Unlike nfost carriers, pyridine is water-soluble and is
.

result of photo-oxidation at the methylene bridge, to

readily removed from the aramid fibers by washing with yield chromophores of the type
’

water. No residual odor is noted after a nominal rinse,

whereas a vigorous scour is usually required to remove
acetophenone [~, 11], henzaldehyde, etc. Unremoved ...

carriers-e.g. benzyl alcohol-are known to adversely incorporation of a light stabilizer in MDA-J fiber can
effect, dyed lightfastness of certain fibers. Thus, the raise the light stability of the natural-colored fiber to
ability to remove pyridine to undetectable levels may nearly pag with Nomex (Table Il.
on ,

be a factor in the excellent dyed lightfastness results A fiber, BAA-I, similar in structure to MDA-I but
observed.
&dquo;

The brightness of the dyed fibers and fabrics is quite

having instead of the o~idativelv-unstable -~H2-
CH3
high when the undyed fibers are bright (e.g. lomev). .
,

i
In the case of certain deep shades (e.g. hlue and red)
the dyed fabrics can be quite bright even when the
bridge a more stable bridge, --C-, was found to resist
! ,
undyed fibers are internally delustered (e.g. wet-spun .

CHa
MDA-1); provided that the fibers have a smooth color formation (Table I) on exposure to light much
surface. better than MDA-I with stabilizer, and, in fact, better
Blank dyeing of the Nomex and MDA-1 fibers does even than Nomex,.
not influence the shade changes (i.e. Gray Scale Ratings)
noted after exposure of the fibers to light (Xenon arc
in a Fade-Ometer).44 Tensile properties of Nomex-and LIGHT STABILITY OF COMMERCIALLY-DYED ~OMFX
CARPET SPECIMENS. Specimens of commercial Nomex.
lB’IDA-I fibers are ~ not adversely effected by solvent
were exposed in the and found to
dyeing. On the contrary, tensile properties are on carpet Fade-Omete~
which became visibly quite
balance improved (see section below on annealing of develop a yellow coloration,
noticeable on relatively- short exposure times and re-
aramid fibers).. _

sulted in poor Gray’Scale Ratings (Table II). The

1.
’

..

but
, DIF;D LIGHTFASTNESS OF ARAMID FIBERS. The natural yarn in one of the specimens turned yellow,
dyed lightfastness of aramid fibers is highly affected by the new color, whileofclearly different from the original,
the following factors : the resistance of the natural fiber was not unpleasant itself. One specimen with yellow
with
toward discoloration by light, the method of dyeing, the yarn in it appeared only to change to a carpet
with blue
depth of shade developed (i.e. amount of dye present), more yellow present. faded carpet sample and to an The
and the type of dye used. The last factor is very im- present initially rapidly quite obviously ’

objectionhble shade. .

4 Operated in accordance with AATCC Method 16E; the rela-

tive humidity and black-panel thermometer temperature main- 5 In-line
dyed in the gel state to deep shades during wet-
tained during the tests were. respectively, 30 &plusmn;5% and 63 &plusmn; 3&deg;C.spinning.

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 286

TABLE I. Gray Scale ratings of aramid staple fibers.*’*’ because the Nomex specimens initially were deeper in
color than the MDA-I ones (for reasons mentioned
already in connection with molecular weights and end- ’

groups of both polymers). ,0#

ANNEALING OF ARAMID FIBERS. Fibers of MDA-I

and Nomex E-19 were found to undergo relaxation
, upon annealing during blank-dyeing. Thus, these
fibers lose a small amount of tenacity but increase
All of the fibers were as-spun; i.e., they were not blank-dyed
significantly in denier and elongation-to-break (Table
a
,

in pyridine prior to exposure in the Fade-Ometer.

b
Results for blank-dyed fibers were the same as for as-spun IV). For the approximately 10 dpf staple Nomex, the
fibers (see Table III for- resu on natural carpet specimens) ; dverdge elongation-.to-break value before blank-dyeing
BAA-I fiber was not tested af er b k-dyeing in pyridine because
of its solubility m that solvent. ~
’
was about the same~as that akter. However, the range
of the value obtained after annealing was. narrowed
&dquo;

For key to ratings and color changes, see Table III.

C
’

d
Spun with incorporation of Uvinul D-50 (2,2’4,4’-tetrahy- considerablv. &dquo;

droxybenzophenone), product of GAF Corp. ’

The shrinkage that occurs during annealing (or

’
’

~ . relaxation) accompanying dyeing suggest that yarns

TABLE II. Gray Scale ratings of Nomex and fabrics may be reasonably stabilized toward further
.
commercial carpet specimens. shrinkage on repeated launderings. Thus, the steam-
ing.or autoclaving with steaming that is reported ~~, 11~

TABLE IV, Tensile properties of aramid fibers after blank-dyeing,

For key to ratings and color changes, see Table III.

’’ An overall yellow color developed, whereas originally there .

were yellow flecks.’ ,

The natural-colored
&dquo;
regions developed a pronounced yellow
color. ~ .

, .

~
a
Obtained on Nomex E-19 sample was
single filaments; the ’

as-received staple from a commercial bale. ’

b
.
Light Stability of 6o~CM/-D~ Carpet Specimens. T =
tenacity, gpd; E elongation-to-break, %; 111 initial
= =

Dyed lightfastness values for Nomex and MDA-I modulus, gpd; den den/filament.
=
,
,

c
1 gpd =
88.26 kN ~ m/kg; 1 mN/tex = 1 kN ~ m; kg; 1 den
carpet specimens are given in Table III. In general, =1.11 dtex.
d A
the dyed Nomex specimens gave somewhat higher Gray very wide range of elongation-to-break values were observed
.

Scale ratings than did the MDA-1 specimens after com- -i.e., 20-120°~0; the average value before blank dyeing w~s
47.6% but the ~rtcan was significantly lower.
parable exposure times in the Fade-Ometer, probably Variations were considerable before annealing. °
~

I
r
.
’ ’ ~~ ~.... ~ ~~~
TABLE III. Dyed lightfastness of solution-dyed carpet specimens.. .
0

. ~(

~
, ..
’

a
Gray scale ratings: 5, none; 4, slight; 3, noticeable; , considerable; 1, much changed. Color change designations are: D =,duller; ’

Y
b
=
yellower; G =
greener; W
weaker. =
: ~
The designations navy, gold, and maroon are us to indicate heavier shade development on the Nomex samples relative to, re-
a~i
~
--

spectively, blue, yellow, and red on the MDA-1 samp es; the same dyes were used on both Nomex MDA-I. ’

....
’
- ’ ,
.
_

. ....

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 287

to be necessary for Nomex fabrics may be unnecessary, perature of treatment in a higher-tailing tertiary amine
~,nd the pilling propensity of the fabrics dyed using the base, such as quinoline, did not increase the tensile I

’
solvent-dyeing method could be reduced. strength or modulus of the X-500 fiber.
The rigid, rod-like fibers, the du Pont Company’s
Kevlar* aramid fibers based on the polyterephthal- ACKNOWLEDGMENTS. The authors wish to acknowl-
amide of p-phenylenediamine (PPD-T), ’and the edge the very substantial contribution of Mr. E. W.
Monsanto Company’s experimental X-500 fiber, based Folk for the spinning of the experimental fibers MDA-I
on the
polyterephthalamide-hydrazide of p-amino- and BAA-I and for providing the dyes used. The
benzI’1ydrazide (PABH-T), do not show (Table V) the comments and suggestions of Drs. J. H. Saunders and
same relaxation trends ’

, W. B. Black on the manuscript are gratefully

acknowledged. ,
Literature Cited
1. Anon., Cationic Dyeing on Non-Flammable Nylon, Canadian
Textile J. 92 (2) 64-65, (1975).
2. Beal, W., Hulme, C., Hobday, C., Jack, J., and Kennan,
J. F. E., "Process for the Dyeing of Aromatic Polyamide
on’annealing thbse exhibited by the MDA-I and
as
Fibers," U. S. Pat. 3,713,769, assigned to Ciba-Geigy Corp,
Nomex fibers. Thus’ while elongation-to-break values January 30, 1973.
are essentially unchanged for both Kevlar and X-~00, 3. Carlsson, D. J., Gan, L. H., Parnell, R. D., and Wiles, D. M.,
The Photodegradation of Poly(1,3-Phenylene Isophthal-
tenacity increases for the Kevlar, and the initial modulus amide) Films In Air, .J. Polym Sci., B, 11,
683-688 (1973).
values increase for both fibers after the blank-dyeing or 4. Carlsson, D. J., Parnell, R. D., and Wiles, D. M., The Photo-
annealing process. _

degradation of Poly(1,3-Phenylene Isophthalamide) Films

Under Vacuum, J. Polym. Sci., B, 11, 149-155 (1973).
TABLE V. Tensile properties of Kevlar 5. Du Pont Company, "Dyeing and Finishing Nomex Type 450
Aramid," Bulletin NX-1, May 1976.
’

.
and X-500 after annealing.
6. Hermes, J., "Pretreatment and Dyeing of Shaped Articles
Derived from Wholly Aromatic Polyamides," U. S. Pat.
3,771,949, assigned to Martin Processing Company, Inc.,
November 13, 1973.
7. Kimbrell, J. P., Jr. and Chantrey, G., "Process of Increasing
the Dye Receptivity of Undyed Polyamide," U. S. Pat.
3,595,606, assigned to the Monsanto Company, July 27,
1971.
8. Magat, E. E., "Polycarbonamides of Improved Dye Affinity
a
Obtained on single filaments. ·
b T
tenacity, gpd;.E = elongation-to-break, °Jo; 3f initial Having the Benzene Sulfonic Acid Salt Moiety as a Integral
= =
Part of the Polymer Chain," U. S. Pat. 3,184,436,
assigned
niodulus, gpd; den den/filament. - =
,

to the du Pont Company, May 18, 1965.

,°1 1 glxi 88.26 kN ~ m/kg; 1 mN/tex
=
1 kX’m/k~; 1 den =

= 1.11 dtex. - ~
,
9. Matsuda, S. and Oshima, T., "Process for Dyeing Aromatic
d The range of the tenacity and elongation-to-break values were Polyamide Fibers," U. S. Pat. 3,591,327, assigned to Asahi,
narrowed compared to!the as-spun samples. July 6, 1971.
10. Richardson, A. J.and Walck, R. E., Jr., "Process for Dyeing
Drawn Filaments of Aromatic Polyamides with Basic Dye-
it’is well known that heating at elevated
Although stuffs in the Presence of an Organic Dye Carrier," U. S.

temperatures increases the tenacity of the~>B

temperatures increases the tenacity of the rigid, rod-like Pat. 3,506,990, assigned to the du Pont Company, April 21,
polymers PPD-T and’poly-~-benzamide ’B), rod-like.. 1970.
11. Schumm, R. W. and ruz, C. J., Dyeing and Finishing Nomex
Nylon, Color. 1 (18) 388/37-30/391 (1969).
.._
_
-f-
NH co :T TextileChenist
12. Teijin, Ltd., "Dy ing Polyamide Fibers with Low Dye-
.
’

PPB
PPa ability," Japan Rat.
73 17, 226, May 28, 1973.
’ . , : ..~· ,
,
.
;
,
.

,
13. Wolf, G. D., M’ ssen, R., Kunzel, H. E., and Bentz, F.,
it is somewhat surprising that heating in pyridine at the "Dyeing Dry-Spun Aromatic Polyamides," U. S. Pat.
boil (-- 105’C) has a significant effect on increasing the 4,066,396, Ja ary 3, 1978.
’, A
tenacity of. Keylar (Table V). Increasing the tem-
.
’

~
Manuscript recei~r~d October 5, 1978.

.>
,

~ .,

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