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Biological and Chemical Research, 1-10 | Science Signpost Publishing

Dyeing of Stockings of Spandex/nylon Core Yarns with

Disperse Dyes in Supercritical CO2 Fluid

Li Zhenhua, Zheng Guanghong, Wu Kun, Ren Jianhua, Zheng Xiong, Bo Yan, Li Guoli, Huang Jun
Chengdu Textile College, Chengdu, China; postcode: 611731

Received: November 01, 2017 / Accepted: December 02, 2017 / Published: January 25, 2018

Abstract: In the paper the dyeing of stockings made from spandex/nylon core yarns in supercritical carbon dioxide fluid

(SCF) with disperse dyes that are affinitive to both components of the yarns is discussed. Dyeing result shows SCF

functions well as a detergent in the stockings’ pretreatment including oil cleaning and inner-stress relief. As a medium,

SCF can dissolve the dye and levelly add color onto the stockings at a relatively high yield with a given color fastness

under a proper control of dyeing temperature, pressure and time. Color yield and fastness are subject to the dye applied.

Color fastness can also be improved by removing unfixed dye from the stockings with SCF. The SCF dyeing method,

which is water-free and environmental-friendly, is applicable and presents a good prospect in the dyeing of stockings

made from spandex/nylon core yarns.

Keywords: spandex/nylon stockings, dyeing, supercritical CO2 fluid, disperse dye, dyeing conditions and quality

1. Introduction

Supercritical carbon dioxide fluid (SCF) dyeing method has been developed fast because of its zero
wastewater discharge, easy separation of dye from carbon dioxide after dyeing, dye recycle and other green,
environment-friendly features，which meet modern society’s requirement and are attractive to dyeing
industry that has been troubled by wastewater emission for a long time [1]. Research reports show SCF
performs well for synthetic fibers dyeing such as polyester, polypropylene and polyamide duo to the good
solubility of disperse dyes in SCF [2].
Stockings, which are made from the core yarns consisting of spandex inside and nylon outside, are

Corresponding author: Li Zhenhua, Chengdu Textile College, Chengdu, China; postcode: 611731
 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

referred to as “female’s second skin” because of their excellent elasticity and flexibility. The stockings take a
large proportion in today’s market. Both spandex (polyurethane fiber with a Tg (glass transition temperature)
ranging from 50°C to 70°C) and nylon (polyamide fiber with a Tg between 40°C and 50°C) can combine
with disperse dyes by Van der Waals forces and/or hydrogen bonds [3] at relatively low temperature, which
is helpful to keep the stockings’ elasticity and flexibility. Core structure of the yarns also apparently reduces
the stockings’ color difference caused by different color yields between the two fibers. On the other hand,
SCF well dissolves oil and plasticates the fibers [4]. SCF can be applied to the stockings’ pretreatment,
which is a necessary step before dyeing to relax fibers and remove the oil brought in during spinning and
weaving process. SCF dyeing’s in-batch operation is suitable to the stockings. The plastification assists the
stockings to absorb dyes at a relatively low temperature. So, the stockings have the essentials suitable to the
SCF dyeing method. Study in this regard will make it hopeful to produce colored spandex/nylon stockings in
a water-free and environment-friendly way, which generates good socioeconomic benefits.

2. Experiment

2.1 Stockings, dyes and auxiliaries

Stockings: supplied by China Bonus Group, including:

Thick pantyhose: made from spandex/nylon 2070 core yarn, in which nylon: 92.4%; spandex: 7.6%.
Thin pantyhose: whose crotch part made from spandex/nylon 2015FDY core yarn, leg part from 2030DTY;
both yarns consist of nylon at 86.8%, spandex at 13.2%.
Dyes: which were refined disperse dyes, including: Blue 79#; Orange 30# and Red 167#; supplied by
Zhejiang Runtu Chemical Ltd.
Auxiliaries: Carbon dioxide, Fixing Agent R (supplied by Shenzhi Chemical Ltd.)

2.2 Dyeing machine and operation

2.2.1 Dyeing machine:

Which was a 5L-capacity sample machine made by Deyang Sichuang Technology. The machine was
equipped with a loop control system and able to provide two SCF circulations, among them one was between
dye vessel and dyeing vessel, running directly and reversely; another between dyeing vessel and separator in
one way.

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

2.2.2 Operation:

After stockings were loaded in dyeing vessel and dyes in dye vessel, operation was carried out in
accordance with the following sequence: pretreatment – dyeing – cleaning, as shown in Figure 1:

Figure 1. Operation sequence and heating curve of SCF dyeing process.

Temperature
110
90
70
50
30
Pretreatment Dyeing Cleaning
10
0 5 20 50 65 70 100 130 145 150 155 180 190 195
Time min

Pretreatment: which started at room temperature with pumping carbon dioxide into dyeing vessel, and then
heated up to 70°C, followed by a circulation of CO2 fluid between dyeing vessel and separator at a given
pressure and temperature for 30min.
Dyeing: which started at 50°C with carbon dioxide pumped from dye vessel into dyeing vessel up to a
given pressure, then circulated alternatively in direct and reverse orientation between the two vessels for
30min, and then heated up to a maximum temperature, at which directly and reversely circulated for another
30min between the two vessels, finally, cooled to 50°C and discharged into separator from where dye residue
is recycled and carbon dioxide is recovered.
Cleaning: whose operation included: at 50°C fresh carbon dioxide was pumped into dyeing vessel to a
given pressure, and heated up to 60°C, and then circulated for 30min between dyeing vessel and separator,
where dyes was separated from carbon dioxide. After the circulation and separation, temperature decreased
to 400C, carbon dioxide was discharged and recycled, and then stockings were unloaded.

2.3 Test instrument and method

Deoiling effect: which was the result by assessing self-made oil-stained stocking samples treated with SCF
in accordance with China’s Gray Scale for Assessing Change in Color on Textiles, GB/T251-2008, in which
grade 5 was the best and grade 1 was the worst.
K/S value: which was the result of measuring dyed stocking using E620-G645/4G Color Measuring and
Matching Instrument made by Fangzheng Wenxiang Ltd.

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

Rubbing fastness: which was measured using YB-571B Textile Rubbing Fastness Tester made by
Wenzhou Darong Textile Instrument Ltd in accordance with GB/T 3920-2008 Textiles-Tests for color
fastness-Color fastness to rubbing, China.
Washing fastness: which was measured using SW-12B Wash Fastness Tester made by Nantong Sansi
Electromechanics Ltd. in accordance with GB/T 3921-2008 Textiles-Tests for color fastness-Color fastness
to washing, China.

3. Result and discussion

3.1 Pretreatment

The pretreatment aimed at ensuring a uniform dyeing by releasing fiber inner stress and removing from
the stockings the oil and stains incurred during spinning and knitting process. It was found that pressure,
temperature, time and circulation of SCF were the factors that impacted deoiling effect. Deoiling grade
increased with the increase of pressure as shown in Figure 2, due to the increase of solubility of oil in SCF
with the increase of SCF density. Heating speeded up the dissolution of oil in SCF, but may decrease the
solubility of oil in SCF, leading to deoiling grade no longer increase with the increase of temperature after a
maximum point. Influence of time on deoiling grade was shown in Figure 3. In a closed vessel dissolution of
oil in SCF would soon reach an equilibrium at which oil no longer dissolved in SCF. In order to break the
equilibrium, a circulation between dyeing vessel and separator was introduced, including the change of
carbon dioxide fluid from supercritical state to none-supercritical one in which oil solubility greatly reduced.
Based on the state change it was available to separate oil from SCF. Test result showed the circulation was
effective in oil removing.
Inner stress of the fibers was released by the action of heating and the plasticization of SCF during the
pretreatment process.

Figure 2：Effect of temperature and pressure Figure 3：Effect of time on deoiling

on deoiling （600C）
5 deoiling
5
deoiling grade
grade 4
4
3 12MPa 3 15MPa
2 16MPa 2 20MPa

1 20MPa 1 25MPa

50 60 70 80 15 20 25 30
Temperature：0C Time（min)

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

3.2 Dyeing
SCF dyeing, like other conventional methods, needed to ensure a uniform coloration. Apart from the
circulation between dye vessel and dyeing vessel that produced a uniform dye solution and kept dye
absorption by fibers in a uniform way, temperature, pressure and dyeing time were the factors that influence
dyeing result, in particular, the color yield. The influences of the factors were discussed as below:

3.2.1 Influence of temperature on color yield

Temperature had a significant influence on the K/S value of the stockings dyed in SCF [5]. Figure 4, 5 and
6 shows the K/S values increased fast with the increase of temperature within the range of 60°C to 90°C,
then slowly from 90°C to 110°C. The influence reflected that above the Tgs of polyurethane and polyamide
fibers there was a fast dye up take during dyeing process. So, in order to have the stockings dyed uniformly,
proper temperature control was needed, as well as other leveling measures such as having a uniform solution
of dye in SCF. The dyeing process was designed to be starting with a low initial temperature at which carbon
dioxide was pumped through dye vessel into dyeing one, and circulated between the two vessels for 30 min,
aiming at having a uniform dye solution and an uniform absorption on the fibers, then heated up at a given
rate to a maximum dyeing temperature at which circulated for another 30min. Heating at a given rate was
aimed at dye’s up-take control, and circulation at maximum dyeing temperature at dye’s exhausting. The
maximum dyeing temperature ranged from 95°C to 100°C, higher than which, the stockings’ performance
such as elasticity would be deteriorated.

Figure 4: Influence of temperature on K/S value

Figure 5: Influence of temperature on K/S value
of thick stockings
20 of crotch part of thin stockings
K/S value 19
18 K/S value
Red
17 Red
167
16 167 15 Orange
Orange
14 30#2
13 30#2
Blue 79
12 Blue 79 11
10 70 80 90 100
70 80 90 100 Maximum temperature 0C
Maximum temperature 0C

Figure 6: Influence of temperature on K/S Figure 7: Influence of pressure on K/S value of

thick stockings
value of leg part of thin stockings 19
21 K/S value
17 Red
K/S value
Red 167
15 167
13 Orange
16 11
30#2
Orange Blue
30#2 9 79
Blue 79
11 13.5 17.9 25.1 28.8
70 80 90 100 Maximum pressure：MPa
Maximum temperature 0C

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

3.2.2 Influence of pressure on color yield

Effect of pressure on K/S value of the stockings dyed in SCF was shown in Figure 7, 8 and 9. All figures
indicate that there was a pressure range that was not wide but produces the highest K/S value. Before
reaching the range K/S value increased with the increase of pressure. After the range K/S value slightly
decreased with the increase of pressure. The variation of K/S value reflected that dye solubility increased
with the increase of SCF density, which was the result of the increase of pressure. In a dyeing vessel, with
the increase of pressure more and more dyes were dissolved in SCF until exhausted [6]. After the exhaust,
excessive increase of SCF density or pressure leaded to excessive dye solubility. The Excessive solubility not
only meant the need of excessive power consumption but the move of dyeing equilibrium towards dye
dissolution from stockings. So, it was necessary to determine an optimized pressure range (18-25 Mpa, for
example) in SCF dyeing.

Figure 8: Influence of pressure on K/S value of Figure 9: Influence of pressure on K/S value of
crotch part of thin stockings leg part of thin stockings
19 20
K/S value
Red K/S value Red
167 167
14 Orang
e 30#2
15 Orange
Blue 30#2
9 79 Blue 79
10
13.5 17.9 25.1 28.8
13.5 17.9 25.1 28.8
Maximum pressure：MPa
Maximum pressure MPa

3.2.3 Influence of time on color yield

Experiment results show at the maximum temperature the dyeing was able to reach its equilibrium in 20
min as shown in Figure 10, 11 and 12. The dyeing speed was relatively quick. SCF was of the characteristics
including excellent dissolving capacity for dyes, low viscosity, good penetrability, weak bond force with dye
molecules, thin diffusion layer formed on fiber, which formed a circumstance in favor of dye absorption and
diffusion on fiber [7]. On the other hand, holding for sometimes the equilibrium, in which dye absorption and
desorption carried on simultaneously, was benefited to a leveling dyeing. So, a bit extension of dyeing time,
for instance, keeping the maximum temperature for 30min, was proper.

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

Figure 10: Influence of time on K/S value of Figure 11: Influence of time on K/S value of
thick stockings crotch part of thin stockings
19
18
K/S value
17 Red K/S value Red
167
16 167
15 Orange
30#2 Orange
13 Blue 79
14 30#2
Blue 79
11 12
15 20 25 30 15 20 25 30
Time at maximum temperature min Time at maximum temperature min

Figure 13: Effect of Solubilizer X on K/S value of

Figure 12: Influence of time on K/S value of leg thick stockings
part of thin stockings
20 20
K/S value K/S value
18 Red 18
167 Red
167
16 Orang 16 Orange
e 30#2 30#2
14 14
Blue Blue
12 79 79
12
15 20 25 30 1 3 5 7
Time at maximum temperature min Quantity of Solubilizer X added g

3.3 Color fastness and Fixation

Table 1 and 2 shows the problem that color fastness of nylon dyed with disperse was lower than that of
polyester fabrics still existed in SCF dyeing, in particular, the FDY and DTY much lower. Measures to
improve the color fastness had to be applied, including:
Dye selection: in which it was found that some of the disperse dyes, for example, Orange 30#2, provided a
good color fastness with the stockings. Orange 30#2 had a bigger molecular mass than others, resulting in
stronger intermolecular forces with fibers.
Cleaning: which was another measure to improve color fastness with the use of SCF to remove unfixed
dye from the stocking fibers. Circulation between dyeing vessel and separator attached a very importance to
the cleaning process as it provided a good unfixed-dye washing-out tool to the closed system.

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

Table 1. Washing fastness of the stockings

Fastness Fastness to wash

Before cleaning After cleaning

Thick Crotch part of Leg part of Thick Crotch part of Leg part of

Disperse dye stockings thin stockings thin stockings stockings thin stockings thin stockings

Red 167 3.0 2.5 2.5 3.5 3.0 3.0

Orange 30#2 3.5 3.0 3.0 4.0 3.5 3.5

Blue 79 3.0 2.5 2.5 3.5 3.0 3.0

Table 2. Dry and wet rubbing fastness of the stockings

Fastness Dry rubbing fastness Wet rubbing fastness

Before cleaning After cleaning Before cleaning After cleaning

Thick Crotch Leg Thick Crotch Leg Thick Crotch Leg Thick Crotch Leg

stock-i part of part of stock-i part of part of stock-i part of part of stockin part of part of

ngs thin thin ngs thin thin ngs thin thin gs thin thin

stock-i stock-i stock-i stock-i stoc-ki stock-i stock-i stock-i

ngs ngs ngs ngs ngs ngs ngs ngs

Disperse dye

Red 167 3.0 2.5 2.5 3.5 3.0 3.0 2.5 2.0 2.0 3.0 2.5 3

Orange 30#2 3.5 3.0 3.5 4.0 3.5 3.5 3.5 3.0 3.0 4 3.5 3.5

Blue 79 3.0 2.5 2.5 3.5 3.0 3.0 2.5 2.5 2.5 3.5 3 3

Fixation: which is an aqueous solution treatment inserted in the setting process of the stockings. After
dyeing, the stocking is treated with a modified cationic polyurethane solution of 20g/L, then dewatered, dried
and set. The treatment is able to improve color fastness by half to one grade in general as shown in Table 3
and 4, because the cationic polyurethane is of the function groups, which react with the hydroxies and
acylaminoes of disperse dye or polyamide fiber, polyurethane fiber; forming a polymer film to seal the dye in
the stockings.

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

Table 3. Washing fastness of the stockings

Fastness Fastness to wash

Before fixation After fixation

Thick stockings Crotch part of Leg part of thin Thick stockings Crotch part of Leg part of thin

Disperse dye thin stockings stockings thin stockings stockings

Red 167 3.5 3.0 3.0 4.0 3.5 4.0

Orange 30#2 4.0 3.5 3.5 4.5 4.0 4.0

Blue 79 3.5 3.0 3.0 4.0 3.5 4.0

Table 4. Dry and wet rubbing fastness of the stockings

Fastness Dry rubbing fastness Wet rubbing fastness

Before fixation After fixation Before fixation After fixation

Thick Crotch Leg Thick Crotch Leg Thick Crotch Leg Thick Crotch Leg

stock-i part of part of stock-i part of part of stock-i part of part of stockin part of part of

ngs thin thin ngs thin thin ngs thin thin gs thin thin

stock-i stock-i stock-i stock-i stoc-ki stock-i stock-i stock-i

ngs ngs ngs ngs ngs ngs ngs ngs

Disperse dye

Red 167 3.5 3.0 3.0 4.0 3.5 4.0 3.0 2.5 3 3.5 3.5 3.5

Orange 30#2 4.0 3.5 3.5 4.5 4.0 4.0 4 3.5 3.5 4.5 4.0 4.0

Blue 79 3.5 3.0 3.0 4.0 3.5 3.5 3.5 3 3 4.0 3.5 3.5

4. Conclusion

1. Stockings made from spandex/nylon core yarns were dyeable with disperse dyes in SCF.
2. SCF was able to play a role not only as a dyeing medium, but as an agent for pretreatment and
post-dyeing cleaning.
3. It was an effective way to remove oily stains or unfixed dyes from the stocking using SCF circulation
combined with separation.
4. Exact control of temperature and pressure was needed to have a uniform dyeing with good color yield.

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 Dyeing of Stockings of Spandex/nylon Core Yarns with Disperse Dyes in Supercritical CO2 Fluid

5. Color fastness can be improved by selecting proper dyes and post-dyeing cleaning.
6. An additional aqueous fixation step was required, which can be inserted in the stockings’ setting process,
along with the use of reactive polyurethane fixing agent.

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[3]. Song Xinyuan, Structure, Property and Dyeing of Polyamide Fiber, China Dyeing and Finishing, 2002, No.11:

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[4]. Ma Yueqi, Long Jiajie, Zhao Jianping, Cheng Ankuang, Effects of Supercritical CO2 Fluid on Polyamide-6 Fibers,

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