Fibre Chemistry, Vol. 44, No. 5, January, 2013 (Russian Original No.

5, September-October, 2012)

STUDY OF PROCESSES OF DYEING POLYURETHANE

FIBRES BY VARIOUS CLASSES OF DYES

A. E. Tret’yakova, V. V. Safonov, UDC 677.027.42

and A. Yu. Yusina

Processes of dyeing polyurethane fibres with various classes of dyes, e.g., disperse and cationic, procinyl
and acid, etc., were studied. Relationships of dyeability with dyeing temperatures were derived and
kinetic and diffusion parameters of dyeability were investigated. Parallel studies of polyester, polyamide,
and polyacrylonitrile fibres, and of wool were made for a comparison. The influence of dyeing conditions
on the physicomechanical strength of polyurethane fibre was examined. The stability of the obtained
colors on polyurethane fibre against external service impacts is evaluated.

Development of polyurethane (PU) fibres (spandex, lycra, etc.) dyeing technology and study of the structure
and properties of the fibres are of great scientific and practical interest. Use of PU fibres in the textile industry is
promising: addition of 3-5% of PU fibres to natural fibres prevents occurrence of such undesirable effects as shrinking,
crumpling, crimping, and creasing. Articles containing PU fibre acquire additional elasticity, do not crumble, and are
pleasant to the touch. The range of elastomeric fibres (filaments) depends on the purpose of their use: either as supplement
for throwing (joining) or as wound threads of other types, and also are an irreplaceable component in production of
materials and textile articles that surround the body (tricot sportswear, haberdashery, medical, etc.) [1-3]. The range of
blended textile materials that contain PU fibre is quite wide (cotton, wool, polyamide, polyester, polyacrylonitrile, etc.).
PU fibres are highly elastic; their rupture elongation reaches 800%, they are resistant to acids, alkalis, and
organic solvents, and fairly resistant to abrasion, light and weather proof. The glass transition temperature of elastomeric
PU fibres ranges from -40 to -60°C and fusion temperature ranges from 160 to 230°C [4-9].
The basic problem of dyeing textile materials containing PU fibres is that even when the same class of dyes is
used for dyeing, the dyeability of the components differs. This causes uneven coloring of the material. In view of this,
it is essential to investigate single-bath dyeing process using one of the following classes of dyes: active acid, disperse,
cationic, and procinyl (active disperse).
It is known from the literature [5] that PU fibres are dyed in acid medium. We dyed PU fibres with acid and
cationic dyes in acid medium and with disperse and procinyl dyes in neutral medium.
The dyeability was determined from the reflectance spectra and corresponding Gurevich−Kubelka−Munk function
obtained on a Minolta (Japan) spectrophotometer using Orientex software (Italy). The correlation curves were constructed
in the form of trends of a 2nd degree polynomial nature, which are the root-mean-square deviation of experimental points.
The influence of temperature and the kinetic and diffusion parameters of the PU fibre dyeing process were
studied. In view of the fact that the dyeing temperature must be higher than the glass transition temperature, the chosen
experimental temperature range was 0-100°C.
With reference to disperse red-brown and cationic blue O (Figs. 1 and 2) it can be seen that dyeability increases
with elevation of dyeing temperature to 60-80°C and the color intensity decreases with further elevation of temperature.
A similar situation is noticed in the case of PU fibre dyeing with dyes of other classes as well.
To determine the kinetic parameters, 60°C was chosen as the temperature on power and heat saving considerations.
Simultaneously was determined, for a comparison, the change in the intensity of color with time also of other fibres for

A. N. Kosygin Moscow State Textile University. E-mail: svv@staff.msta.ac.ru. Translated from Khimicheskie
Volokna, No. 5, pp. 24-27, September-October, 2012.

284 0015-0541/13/4405-0284 © 2013 Springer Science+Business Media New York

 14 10
12
8
10
6 1
8

k/s
6 4

k/s
4
2 2
2
0 0
0 20 40 60 80 t, °C 100 0 20 40 60 80 t, °C 100

Fig. 1. Fig. 2.
Fig. 1. Influence of temperature on dyeability of PU fibres dyed with disperse red-
brown (red-cinnamonic) dye.

Fig. 2. Influence of temperature on dyeability of PU (1) and polyacrylonitrile (2) fibres

dyed with cationic blue O.

25 16
1
20
12
15 2
8
k/s

k/s
10
2 1
5 4

0 0
0 20 40 60 80 τ, min 100 0 20 40 60 80 τ, min 100

Fig. 3. Fig. 4.
Fig. 3. Kinetics of PU (1) and PA (2) fibre dyeing with bright-pink dye.
Fig. 4. Kinetics of dyeing PAN (1) and PU (2) fibres with cationic red.

30
25
1
20
15
k/s

2
10
5
0
0 20 40 60 80 100 τ, min

Fig. 5. Kinetics of dyeing wool (1) and PU (2) fibres

with procinyl orange.

which the test dyes have affinity: acid dyes for wool, cationic dyes for polyacrylonitrile (PAN) fibre, disperse dyes for
polyester (PE) and polyamide (PA) fibres, and procinyl for polyamide fibre.
Note that in almost all cases the dyeability of PU fibre was 2-4 times greater than that of other fibres regardless
of the dye class, as shown by the example of PU and PA fibre dyeing with disperse bright-pink dye (Fig. 3). Because of
the relatively low dyeing temperature and the structural peculiarities (highly packed supramolecular structure), very low
(roughly 5.5 times lower) dyeability is typical for PE fibre.
In the case of PAN and PU fibre dyeing with cationic red 2C, the pattern of kinetic dependence of dyeability is
similar, i.e., the color intensity increases (Fig. 4). Note that the color intensity of PU fibre is roughly 2-2.4 times higher
than that of PAN fibre.
An exception was procinyl, dyeing with which shows a dramatic increase in dyeability of PU fibre over 1-10
min, after which the color intensity diminishes gradually (Fig. 5). Such a situation differs completely from the traditional
(in the case of other fibres) relationship in the coordinates k/s = f(t), where k is the absorption coefficient, which is

285
 Table 1. Diffusion Parameters of Dyeing Process

PU PA Wool PAN PE
Dye R = 4.5 μm R = 1.5 μm R = 1 μm R = 1 μm R = 2 μm
D⋅10-16, m2 /sec D⋅10-16 , m2/ sec D⋅10 -1 6, m2 /sec D⋅10-16 , m2/ sec D⋅10 -1 6, m2 /sec
6
Disperse bright-pink 212.63 8.78 – – 32.31
Acid bri ght-blue anthraqui none 10.63 23.63 – – –
Catio nic blue O 212.63 – – 0.81 –
6
Catio nic red 2C 212.63 – – 3.5 –
Procinyl scarlet 212.63 – 2.14 – –
Procinyl orange 212.63 – 1.18 – –
______________
Note: R - fibre radius and D - dy e diffusion rate.

Table 2. Stability of PU fibre Color against Washing

Dye Po int
Disperse bright-pink 4/1
Acid bri ght-blue anthraquinone 4/5
Procinyl scarlet 4/4
Procinyl orange 5/4
Cati onic red 2C 5/4
Cati onic bl ue O 3/2

proportional to the dye content in the fibre, and s is the scattering (dispersion) coefficient. It can be suggested that
procinyl and PU fibre react chemically, which alters the usual pattern of the kinetic relationship of diffusion of the dye
into the fibre.
In order to determine the diffusion parameters of PU fibre dyeing, comparative characteristics were tabulated
(Table 1) with reference to the diffusion rate for each of the investigated fibre. From Table 1 it can be seen that the rate
of diffusion of disperse and cationic dyes and procinyls increases in the PU fibre. In the case of acid dyes, the diffusion
rate for PA fibre is twice higher.
The change in PU fibre dyeing temperature from 0 to 100°C is accompanied by a change in the physicomechanical
parameters if account is taken of the glass transition temperature between -40 and -60°C. Because of this, an analysis
was made of the mechanical strength, such as the rupture load, of the PU fibre dyed with the investigated dyes in the
above-noted temperature range. Note that the rupture load of undyed PU fibre is 0.9 N.
Determination of the mechanical strength of PU fibre demonstrated that the maximum rupture load is observed
when dyeing at 40-60°C with disperse dyes and procinyls. In the case of dyeing with acid dyes, the temperature does not
exert appreciable influence on the fibre strength. The best rupture load indices are noted in the case of dyeing with
cationic dyes between 20 and 60°C, in which case the rupture load does not exceed that of the original, undyed PU fibre.
The most important criterion of any of the obtained colors is its stability against external impact under service
conditions, especially against washing done very frequently in domestic situations. From Table 2 it can be seen that
fairly high stability of PU fibre color can be attained when dyeing is done with acid bright-blue anthraquinone, cationic
red 2C, and procinyls.
Thus, for dyeing PU fibre, out of the dye classes we recommend primarily procinyl and acid dyes which ensure
fairly bright and fast color.
Note that the developed condition of dyeing with a single class of dyes is promising for blended variety of
textile materials containing PU fibre. It includes variation of such parameters as temperature, duration, pH, nature of
textile ameliorating agents which ensures maximum dye fixation and fastness of the obtained color with full retention of
the physicomechanical properties of the fibre.

286
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