Article

Kinetics of Low Temperature Polyester Dyeing with

High Molecular Weight Disperse Dyes by Solvent
Microemulsion and AgroSourced Auxiliaries
Shahram Radei, Francisco Javier Carrión-Fité, Mònica Ardanuy * and José María Canal
Secció Enginyeria Tèxtil, Departament de Ciència dels Materials i Enginyeria Metal.lúrgica, Universitat
Politècnica de Catalunya, C/Colom 11, 08222 Terrassa, Spain; [email protected] (S.R.);
[email protected] (F.J.C.-F.); [email protected] (J.M.C.)
* Correspondence: [email protected]; Tel.: +34-937-398-158

Received: 12 January 2018; Accepted: 14 February 2018; Published: 16 February 2018

Abstract: This work focused on the evaluation of the kinetics of dyeing polyester fabrics with high
molecular weight disperse dyes, at low temperature by solvent microemulsion. This study also
compared the effect of two non-toxic agro-sourced auxiliaries (o-vanillin and coumarin) using a non-
toxic organic solvent. A dyeing bath consisting of a micro-emulsion system involving a small
proportion of n-butyl acetate was used, and the kinetics of dyeing were analysed at four
temperatures (83, 90, 95 and 100 °C). Moreover, the dyeing rate constants, correlation coefficient and
activation energies were proposed for this system. It was found that o-vanillin yielded higher dye
absorption levels than coumarin, leading to exhaustions of 88% and 87% for Disperse Red 167 and
Disperse Blue 79, respectively. K/S values of dyed polyester were also found to be higher for dye
baths containing o-vanillin with respect to the ones with coumarin. In terms of hot pressing fastness
and wash fastness, generally no adverse influence on fastness properties was reported, while o-
vanillin showed slightly better results compared to coumarin.

Keywords: polyester dyeing; microemulsion; o-vanillin; coumarin; n-butyl acetate; kinetics

1. Introduction
Polyester (Polyethylene terephthalate) (PES) fibres are the most used fibres in the global apparel
industry, and therefore are a prominent topic of research. The hydrophobic nature PES fibres,
combined with a glass transition temperature (T g ) of around 80 °C, make their dyeing process
challenging, since it is high-energy and consumes a significant amount of water [1]. The most
common dyestuffs used to dye PES fibres are disperse dyes. These dyes are almost insoluble in water,
making it necessary to use them in combination with dispersing agents and carriers, if the dyeing
processes are performed in water under 100 °C [2,3]. The carriers, which have smaller size than the
dyes, are capable of penetrating the amorphous regions of fibres, like polyester, and opening the
macromolecular structure of the polymer at temperatures higher than the T g . However, the nature
and high molecular weight of the organic compounds used generally as carriers involves problems
of non-biodegradability and toxicity. These agents can also partially plasticize polyester fibres,
decreasing their glass transition temperature [4,5].
Dyeing and avoiding the use of carriers in the conventional industrial process is only possible at
higher temperatures, such as 130–135 °C, to produce a sufficient absorption level. Although this
system is the most used process in the world, it requires costly machinery in relation to the material
processed, and a considerable amount of energy to heat and maintain the dye bath at the operating
temperature [6].

Polymers 2018, 10, 2; doi:10.3390/polym10020200 www.mdpi.com/journal/polymers

Polymers 2018, 10, 2 2 of 12

Recent studies have attempted to look for alternative processes for polyester dyeing with non-
hazardous and more environmentally friendly compounds that also require less energy in the overall
dyeing process. With the aim of avoiding negative effects of the carriers, Harifi and Montazer [7]
studied the effect of nano-TiO 2 on the dyeing process of PES with disperse dyes. They found that the
colour strength of the PES fabric increased by the effect of the pre-treatment, consisting of an
immersion in aqueous dispersions of nano-TiO 2 particles (0.25%–2% (w/v)). This method was free
from the aforementioned disadvantages of carriers, but its industrial application is costly and very
difficult to perform [7].
Choi et al. [8] compared the dyeing behaviour of PES fabrics with Disperse Blue C.I. 56 dye, and
used two environmentally friendly cationic gemini surfactants as auxiliaries, namely propanediyl-
α,ω-bis(dimethyldodecylammoniumbromide) (DC3-12) and hexanediyl-α,ω-bis
(dimethyldodecylammoniumbromide) (DC6-12) or a conventional surfactant
(dodecyltrimethylammonium bromide) (C12C1NBr). The study proved that colour strength with
gemini surfactants was higher than achieved with the conventional one. They found also that
increasing the concentration of gemini surfactants led to a decrease of the dye hydrophobicity above
the critical micelle concentration (CMC). Moreover, it was found that dyeing with gemini surfactants
had benefits such as controlling dyeing kinetics and improving dye absorption by the PES fabric [9].
On the other hand, several studies propose dyeing processes with more environmentally
friendly carriers at temperatures lower than 100 °C. Pasquet et al. [10], used a high concentration of
o- and p-vanillin as carriers for low-temperature dyeing of polyester fabrics (90 °C), with low and
high molecular weight disperse dyes in the presence of ethanol as a co-solvent [10]. This study proved
that o- and p-vanillin can be a substitute for conventional carriers. Additionally, PES fabric dyed with
these carriers presented acceptable absorption and fastness. Furthermore, Pasquet et al. [10] analysed
the toxicity of o- and p-vanillin with the USEtox system, confirming that these carriers are not toxic.
Carrión-Fite proposed a low-temperature dyeing process in the presence of a micro-emulsion
obtained by ultrasonic agitation, composed of a low proportion an alkyl halogen solvent and a
phosphoglyceride emulsifier [11]. In this sense, it was proved that ultra-sonic cavitation improves the
dyeing rate constant, and the dye absorbed by the fibre [12,13].
More recently, Carrión-Fite and Radei [14] proposed the use of more environmentally friendly
dyeing auxiliaries based on o-vanillin or coumarin in an n-butylacetate co-solvent (an organic non-
toxic solvent) for low molecular weight disperse dyes (C.I. Disperse Blue 56 and C.I. Disperse Red 73).
The study confirmed that o-vanillin and coumarin had a positive and significant influence on dyeing
behaviour of polyester in this system. At a temperature of 95 °C, the absorption levels of the fibres
after 120 min were excellent: the content of Disperse Blue 56 dye absorbed by the PES in the presence
of o-vanillin or coumarin was 97% and 96%, respectively. In the case of Disperse Red 73, the amount
absorbed was 81% and 82%, respectively, for of o-vanillin or coumarin. Moreover, wash fastness was
similar to the conventional process of dyeing polyester [14,15]. However, it was necessary to study
more in depth the effect of the carriers by analysing the thermodynamic parameters and heat fastness,
among others, to establish this new methodology. Moreover, another limitation of this study was that
only low molecular weight disperse dyes were analysed.
In this paper, we investigated the kinetics of dyeing PES fabrics with two high molecular weight
disperse dyes (Disperse Red 167 and Disperse Blue 79), in a micro-emulsion system involving a small
proportion of a non-toxic organic solvent (n-butyl acetate), and two potential auxiliaries (o-vanillin
and coumarin). Moreover, the activation energies were determined for this system.

2. Materials and Methods

2.1. Chemicals
The fabric used was a PES 100% woven standard polyester, Type 30 A, from Testgewebe GmbH
(Brüggen, Germany) (ISO 105-F10). The high molecular weight disperse dyes used were Rubi Foron
S-2GFL (C.I Disperse Red 167) and Navy Blue Foron S-BRL (Disperse Blue 79). All dyes were supplied
by Clariant (Prattlen, Switzerland). Coumarin (99% purity) was supplied by Acros (NJ, USA) and o-
Polymers 2018, 10, 2 3 of 12

vanillin (99% purity) was supplied by Acros (NJ, USA). Both carriers use agro-sourced alternative
compounds with additional properties, such as antimicrobial, antioxidant, biodegradability and
antimutagenic. Also, these carriers are hydrophobic with no toxicity, and we expect them to have
better influence on polyester dyeing [10,16]. The chemical structure of these chemicals is presented
in Table 1.

Table 1. Chemical structure of dyes and auxiliaries.

Dyes and Chemicals Chemical Structure

C.I. Disperse Red 167

CAS No. = 61968-52-3/26850-12-4
M W = 519.93 g·mol–1

C.I. Disperse blue 79

CAS No. = 12239-34-8
M W = 639.41 g·mol−1

Coumarin
2H-chromen-2-one
CAS No. = 91-64-5
M W = 146.15 g·mol−1

o-vanillin
2-hydroxy-3-methoxybenzaldehyde
CAS No. = 148-53-8
M W = 152.15 g·mol−1

Pure n-butyl acetate (M w = 116.16 g·mol–1), supplied by Panreac (Barcelona, Spain), was used as
the co-solvent. N,N-Dimethylformamide (M w = 73.10 g·mol–1), 99.8% purity and supplied by Panreac
(Barcelona, Spain), was used as the solvent to extract the dyes from the PES fabrics. Hostapal non-
ionic surfactant detergent, supplied by Archroma GmbH (Sulzbach, Germany), was used as for pre-
dyeing washing. QP-grade 85% pure sodium dithionite (M w = 174.11 g·mol–1) and analytical-grade
sodium hydroxide, both supplied by Panreac, were used as a post-dyeing washing reductant.

2.2. Experimental Methods

2.2.1. Dyeing Procedure

Figure 1 shows the dyeing process for the proposed methodology.
Polymers 2018, 10, 2 4 of 12

Figure 1. Experimental dyeing process used for this study.

PES fabrics were prepared for dyeing by cutting 16 cm in warp and 11 cm in weft, and weighing
3.0 g. Fabric pre-washing was done by using Hostapal detergent at a 0.5 g·L–1 concentration at 40 °C
for 30 min.
The dye bath was prepared by dissolving carriers in n-buthylacetate and then adding the dye
solution. The mixture was stirred for 2 min followed by sonication for 1 min. The bath ratio for each
dyeing operation was set to 1:60. The quantity of dyes and chemicals used were 2% o.w.f. of disperse
dye, 4% o.w.f. of auxiliaries and 3 ml of n-buthylacetate, for a total amount of 180 mL of dye bath.
The dyeing process was carried out in a Linitest dyeing apparatus, furnished with 300 mL sealed cans
that were purchased from Atlas MTT GmbH (Linsengerich, Germany). The dyeing temperatures
were 83, 90, 95 and 100 °C for a fixed time of 120 min. One-half of all tests used o-vanillin and the
other half coumarin as auxiliaries.
After the dyeing process, the samples were rinsed with water two times and dried at ambient
conditions. Post washing was performed in a reductive medium to remove all dye absorbed onto the
fibre surfaces. The reductive medium consisted on a mixture of 0.5 g/L sodium hydroxide and 2 g/L
sodium hydrosulphite in distilled water (bath ratio 1:50). This process was followed by washing at
50 °C for 30 min, rinsing three times with water and drying at room temperature for 24 h.

2.2.2. Colour Fastness

Wash fastness of the samples was tested according to the UNE-EN ISO 105-C06 method. The
samples were washed with IEC 60456 Base Detergent Type A at 40 °C for 30 min, keeping liquor to
material ratio as 1:50. The colour fastness to hot pressing was tested according to the UNE-EN ISO
105-X11 method.
Polymers 2018, 10, 2 5 of 12

2.2.3. Dye Absorption

The amount of dye absorbed by the PES was quantified by spectrophotometric analysis after
dye extraction with N,N-dimethylformamide (DMF). The absorbance at the maximum wavelength in
the visible spectrum is a linear function of the concentration of dye dispersed in DMF following the
Beer–Lambert law. The maximum absorbance was determined for each dye at different
concentrations, obtaining linear regressions with R values ranging from 0.9758 to 0.9845. A model M
330 UV–Visible spectrophotometer was used that was purchased from Camspec (Leeds, UK).

2.2.4. Particle Size Analysis

To evaluate the homogeneity of the dye baths, particle size measurements were performed using
a Zetasizer nano series device from Malvern (Malvern, UK) at 90° with respect to the incident laser
beam at 25 °C [17].

2.2.5. Determination of Exhaustion

The exhaustion was determined using Equation (1):
𝐶𝐶0 − 𝐶𝐶𝑠𝑠
𝐸𝐸𝐸𝐸𝐸𝐸ℎ𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 (%) = × 100 (1)
𝐶𝐶0
where C 0 is initial concentration of dye and C s is final concentration of dye.

2.2.6. Determination of Colour Strength

The colour strength, expressed as K/S value, was determined from the spectral diffuse
reflectance using a spectrophotometer (Gretag Macbeth 7000). Reflectance values of the samples (R)
were used to calculate K/S based on Kubelka-Munk, as shown in Equation (2) [18]:
𝐾𝐾 (1 − 𝑅𝑅)2
= (2)
𝑆𝑆 2𝑅𝑅
where R is the % Reflectance/100 of coloured samples at λ max , and K and S are the absorption and
scattering coefficients, respectively.

3. Results and Discussion

3.1. Emulsion Particle Size

Before dyeing, the particle size of the dye bath emulsions was determined and compared with
the bath in the presence of high molecular weight disperse dyes without any auxiliaries. The average
values are presented in Table 2.

Table 2. Particle size of dyebath in a presence of Coumarin, vanillin and without auxiliaries.

Dye-Bath Average Diameter (nm) Polydispersity

2% o.w.f. Disperse Red 167;
183 ± 9.5 0.153 ± 0.03
4% o.w.f. coumarin & 1 mL/g o.w.f. n-buthylacetate
2% o.w.f. Disperse Blue 79;
160.3 ± 14.2 0.121 ± 0.03
4% o.w.f. coumarin & 1 mL/g o.w.f. n-buthylacetate
2% o.w.f. Disperse Red 167;
236.3 ± 10.97 0.107 ± 0.032
4% o.w.f. o-vanillin & 1 mL/g o.w.f. n-buthylacetate
2% o.w.f. Disperse Blue 79;
249.3 ± 4.5 0.247 ± 0.05
4% o.w.f. o-vanillin & 1 mL/g o.w.f. n-buthylacetate
2% o.w.f. Disperse Red 167 & 1 mL/g o.w.f. n-buthylacetate 238.3 ± 0.6 0.183 ± 0.01
2% o.w.f. Disperse Blue 79 & 1 mL/g o.w.f. n-buthylacetate 250 ± 15.5 0.3 ± 0.05

According to the table, it can be concluded that all dye-baths were in general homogenous:
values obtained were acceptable in this micro-emulsion system. The average for the particle size (200
Polymers 2018, 10, 2 6 of 12

nm) and the mean of polydispersity (0.2) presented standard values for the dyeing process. Particle
sizes of dye-bath in a presence of coumarin showed better results. Indeed, presence of this auxiliary
successfully reduced the particle size. Nonetheless, when o-vanillin was used, no significant changes
in particle sizes were found with respect to the bath without auxiliaries.

3.2. Dyeing Kinetics and Rate Constant

Figures 2–5 show the dyeing kinetics of two single azo class high molecular weight disperse
dyes in the presence of the two auxiliaries used, namely C.I. Disperse Red 167 with 4% o.w.f. of
coumarin (Figure 2), C.I. Disperse Red 167 with 4% o.w.f. of o-vanillin (Figure 3), Disperse Blue 79
with 4% o.w.f. of coumarin (Figure 4) and Disperse Blue 79 with 4% o.w.f. of o-vanillin (Figure 5).

100

80
Exhausion (%)

60

40

20

0
0 50 100 150

Time (min)

100 ºC 95 ºC 90 ºC 83 ºC

Figure 2. Dyeing kinetics for polyester (polyethylene terephthalate) (PES) fabric dyed with Disperse
Red 167 and Coumarin.

100

80
Exhausion (%)

60

40

20

0
0 50 100 150
Time (min)

100 ºC 95 ªC 90 ºC 83ºC

Figure 3. Dyeing kinetics for PES fabric dyed with Disperse Red 167 and o-vanillin.
Polymers 2018, 10, 2 7 of 12

As shown, the initial dyeing rate of coumarin was slightly higher than o-vanillin at almost all
temperatures, but the final rate of o-vanillin was higher than coumarin. Exhaustion % of o-vanillin at
100 °C after 120 min was 88.0%, which is similar to that achieved during the conventional dyeing
process of polyester at 130–135 °C. Values obtained with o-vanillin were slightly higher than
coumarin, except for 83 °C, in which dye absorption level was higher.

100

80
Exhausion (%)

60

40

20

0
0 50 100 150
Time (min)
100 ºC 95 ºC 90 ºC 83 ºC

Figure 4. Dyeing kinetics for PES fabric dyed with Disperse Blue 79 and Coumarin.

100

80
Exhausion (%)

60

40

20

0
0 50 100 150
Time (min)

100 ºC 95 ºC 90 ºC 83 ºC

Figure 5. Dyeing kinetics for PES fabric dyed with Disperse Blue 79 and o-vanillin.

Concerning the dyeing with Disperse Blue 79, it was found that the initial dyeing rate with
coumarin was significantly higher than for o-vanillin, except at 100 °C. However, after 60 min of the
dyeing process, the PES fabric dyed in presence of o-vanillin presented a higher absorption level. At
100 °C, the values of exhaustion of PES fabric dyed with o-vanillin reached 87% after 120 min, which
is similar to those achieved in the conventional dyeing process of polyester at 130–135 °C, as was
mentioned above for Disperse Red 167.
From these results it can be concluded that o-vanillin leads to higher absorption dyeing levels
than coumarin. This can be due to the higher hydrophilicity of o-vanillin, which makes it more
difficult to diffuse it inside of the amorphous phase of PES. However, once diffused, it leads to higher
absorption.
Tables 3 and 4 indicates K/S values obtained for the dyed polyester fabrics at 100 °C at different
times.
Polymers 2018, 10, 2 8 of 12

Table 3. K/S values for PES fabric dyed with D167 in presence of 0.666 g·L–1 of coumarin or o-vanillin
at 100 °C and different times (5, 10, 30, 50, 70, 90 and 105 min).

T = 100 °C C.I. Disperse Red 167

t (min) 5 10 30 50 70 90 105
Coumarin
K/S λ = 640 nm 4.490 8.820 11.157 16.382 17.025 18.698 19.133
Vanillin
K/S λ = 640 nm 3.487 9.260 13.190 14.934 18.378 19.305 21.383

Table 4. K/S values for PES fabric dyed with D79 in presence of 0.666 g·L–1 of coumarin or o-vanillin
at 100 °C and different times (5, 10, 30, 50, 70, 90 and 105 min).

T = 100 °C C.I. Disperse Blue 79

t (min) 5 10 30 50 70 90 105
Coumarin
K/S λ = 640 nm 3.298 4.807 3.298 4.807 3.298 4.807 3.298
Vanillin
K/S λ = 640 nm 3.877 5.061 6.982 7.741 9.982 11.166 12.08

As expected, the K/S values increased as time increased for both auxiliaries at 100 °C. As seen,
o-vanillin yield higher colour strength than coumarin in all cases. On the other hand, it was found
that disperse Red 167 had higher shade depth compared to Disperse Blue 79. Values of K/S were
almost similar to those achieved in the conventional dyeing process of PES at higher temperatures,
with a range between 12 and 21.
The following equation to calculate the dyeing rate constant and correlation coefficient was used
[11]:
𝑋𝑋 1 − 𝑋𝑋
𝐾𝐾𝑇𝑇 = + 0.5 ln (3)
(1 − 𝑋𝑋) 2 1 + 𝑋𝑋
where x is the quotient between the dye concentration on the fibre at time t and the initial time in the
dye-bath, K is the dyeing rate constant and t is the time of the kinetics examined.
Table 5 shows the dyeing absorption rate constants and their respective correlation coefficients,
calculated from Equation (3).

Table 5. Absorption rate constant (K), correlation coefficient (R2) and exhaustion after 120 min (%) for
the kinetics of dyeing of polyester with disperse dyes in the presence of o-vanillin or coumarin
auxiliaries.

o-Vanillin Coumarin
Exhaustion after Exhaustion after
Disperse Dye K R2 K R2
120 min (%) 120 min (%)
C.I. Disperse Red 167 at 100 °C 0.5667 0.9855 88.21 0.1759 0.9659 81.22
C.I. Disperse Red 167 at 95 °C 0.1712 0.9716 79.78 0.0711 0.9704 71.45
C.I. Disperse Red 167 at 90 °C 0.0426 0.992 65.65 0.0312 0.989 61.96
C.I. Disperse Red 167 at 83 °C 0.0128 0.9523 50.29 0.0153 0.9436 53.45
C.I. Disperse Blue 79 at 100 °C 0.472 0.9764 87.96 0.1892 0.9577 81.42
C.I. Disperse Blue 79 at 95 °C 0.1359 0.9736 78.42 0.0638 0.9268 71.37
C.I. Disperse Blue 79 at 90 °C 0.0722 0.9305 71.95 0.0294 0.934 63.39
C.I. Disperse Blue 79 at 83 °C 0.0208 0.9108 58.34 0.0129 0.9105 53.60413

According to Table 5, the absorption rate constant for both dyes increased with increasing
temperature, as expected. The rate constant values of o-vanillin were considerably higher than
coumarin due to a higher absorption level. Correlation coefficients with the equation used were more
Polymers 2018, 10, 2 9 of 12

than 0.9, demonstrating a good adjustment. In general, values obtained with o-vanillin were more
attractive.

3.3. Activation Energy

The activation energy for each dye during the dyeing process was calculated from the Arrhenius
equation:
K = K 0 e−E/RT (4)
where K is the rate constant, K 0 is the pre-exponential factor, E is the activation energy, T is the
absolute temperature and R is the constant of ideal gases.
Table 6 shows the apparent activation energies for the dyeing of polyester with disperse dyes at
a low temperature by the absorption rate constant obtained from Equation (4).

Table 6. Activation energy (E) and correlation coefficient (R2) for the two dyes studied in the presence
of o-vanillin or coumarin auxiliaries.

o-Vanillin Coumarin
Disperse Dyes E (Kcal·mol )–1 R 2 E (Kcal·mol–1) R2
C.I. Disperse Red 167 59.3 0.9869 37.8 0.9763
C.I. Disperse Blue 79 46.6 0.9841 40.8 0.9781

As can be seen, energies ranged from 37 to 59 kcal·mol–1 and were similar to those previously
reported for the dyeing of polyester with disperse dyes. These values show that temperature
significantly influenced this process. The activation energies of the disperse dyes were higher in the
presence of o-vanillin than coumarin. This means that dyeing PES with o-vanillin requires more
energy to diffuse the dyestuff into the fabric than coumarin. Indeed, the higher the activation energy,
the higher the barrier to diffusion of the dye molecules into the fabric [11,19]. This can be explained
because o-vanillin is more hydrophilic than coumarin, and therefore the penetration inside of the dye
molecules with this auxiliary is more difficult. However, once o-vanillin penetrates, it causes higher
swelling of polyester and makes the diffusion of the dye easier. Finally, it was found that the
correlation coefficients were all acceptable and had values greater than 0.97.

3.4. Washing Fastness

Table 7 shows colour fastness for domestic and commercial laundering for the high molecular
weight dyes according to the standard methodology, and using the A2S test indicated in this standard
[20].

Table 7. Colour fastness by washing of polyester dyed materials.

o-Vanillin Coumarin
PET Fabric Dyed 120 min
Gray Scale PES Cotton Gray Scale PES Cotton
C.I. Disperse Red 167 at 83 °C 4–5 4 3–4 5 4 3–4
C.I. Disperse Red 167 at 90 °C 5 3–4 3–4 4–5 4–5 3–4
C.I. Disperse Red 167 at 95 °C 5 4–5 3–4 4–5 4 3–4
C.I. Disperse Red 167 at 100 °C 5 4–5 3–4 5 4 3–4
C.I. Disperse Blue 79 at 83 °C 4–5 4–5 3–4 4–5 4–5 3–4
C.I. Disperse Blue 79 at 90 °C 4–5 4–5 3–4 4–5 4–5 3–4
C.I. Disperse Blue 79 at 95 °C 5 5 3–4 5 5 3–4
C.I. Disperse Blue 79 at 100 °C 5 4–5 3 5 4–5 3–4

It can be reported that the colour fastness by washing in this dyeing process was totally
acceptable, because there was no adverse influence on fastness properties. Staining of the white
polyester fabric was good for all dyes and auxiliaries tested. With respect to the white cotton fabric,
Polymers 2018, 10, 2 10 of 12

values were almost similar to the regular level. Values of both auxiliaries and disperse dyes were
quite similar, but o-vanillin exhibited slightly better colour fastness by washing than coumarin.

3.5. Hot Pressing Fastness

Dry heat was applied to dyed and undyed polyester fabric at three temperatures (110, 150 and
200 °C) under pressure to measure colour changes and colour migration to the white fabric due to
the steam. Tables 8 and 9 indicate discharge hot pressing fastness and degradation hot pressing
fastness of dyes with higher molecular weight.

Table 8. Degradation hot pressing fastness.

Discharge Hot Pressing Fastness (Gray Scale)

PET Fabric Dyed 120 min
o-Vanillin Coumarin
110 °C 150 °C 200 °C 110 °C 150 °C 200 °C
C.I. Disperse Red 167 at 83 °C 5 5 5 5 5 4–5
C.I. Disperse Red 167 at 90 °C 5 5 4–5 5 5 4–5
C.I. Disperse Red 167 at 95 °C 5 5 4–5 5 4–5 4–5
C.I. Disperse Red 167 at 100 °C 5 4–5 4–5 5 4–5 4
C.I. Disperse Blue 79 at 83 °C 5 4–5 4–5 5 5 4–5
C.I. Disperse Blue 79 at 90 °C 5 5 4–5 5 5 4–5
C.I. Disperse Blue 79 at 95 °C 5 4–5 4–5 5 5 4–5
C.I. Disperse Blue 79 at 100 °C 5 5 5 5 5 5

Table 9. Discharge Hot Pressing fastness.

Degradation Hot Pressing Fastness (Gray Scale)

PET Fabric Dyed 120 min
o-Vanillin Coumarin
110 °C 150 °C 200 °C 110 °C 150 °C 200 °C
C.I. Disperse Red 167 at 83 °C 4–5 3 2 3 2–3 1–2
C.I. Disperse Red 167 at 90 °C 4–5 3 1–2 3 2–3 1–2
C.I. Disperse Red 167 at 95 °C 4–5 4 2 2–3 2–3 2–3
C.I. Disperse Red 167 at 100 °C 4–5 4 2 4 4 4–5
C.I. Disperse Blue 79 at 83 °C 5 3 1–2 3–4 3 1–2
C.I. Disperse Blue 79 at 90 °C 4 3–4 1–2 3–4 2–3 2
C.I. Disperse Blue 79 at 90 °C 4–5 4–5 2–3 3 2 3
C.I. Disperse Blue 79 at 100 °C 4–5 4–5 2–3 4–5 4–5 4

Generally, heat fastness of this dyeing method was positive, and no significant changes can be
seen for the properties. Degradation hot pressing fastness of both dyes and auxiliaries at lower
temperatures, like 83 and 90 °C, were in the regular level (such as 2–3 or 1–2), whereas discharge hot
pressing fastness were in the excellent level, as most values were 5. Polyester fabric dyed in this
process had good heat stability based on the degradation results. In terms of transforming colour
(migration) to the white fabric (discharge hot fastness), the results were in the regular level.
O-vanillin showed remarkably better heat fastness than coumarin, and values obtained with o-
vanillin were more convincing. In terms of two disperse dyes, the results indicated that C.I. Disperse
Blue 79 was better than C.I. Disperse Red 167.

4. Conclusions
Based on the kinetics and K/S analysis, it was found that both auxiliaries at temperatures near
to 100 °C led to a good dyeing absorption level in PES fabrics.
Comparing the two auxiliaries studied, it was found that polyester dyed in the presence of o-
vanillin yielded, in general, a higher absorption level and colour strength than in the presence of
coumarin. Moreover, a higher colour strength was found for Disperse Red 167 compared to Disperse
Polymers 2018, 10, 2 11 of 12

Blue 79. It is understandable that temperature would have a significant influence in this dyeing
system. The effect of temperature on o-vanillin was more apparent, as dyeing PES with o-vanillin
involves more energy to penetrate the polyester fabric than coumarin. Ranges of energies were
similar to those achieved in the conventional process. In terms of applicability and interaction
between fabric and dye molecules, the swelling of polyester dyed with o-vanillin auxiliary was higher
than coumarin; therefore this factor led the fabric to absorb more colour. According to wash and hot-
pressing fastness, the auxiliaries were almost similar to each other. Fastness property results were
positive, and there were no significant changes of the fastness properties. However, polyester fabric
dyed with o-vanillin show slightly better wash and heat fastness than coumarin.
Additionally, we attempted to dye polyester in a manner as ecologically friendly and economical
as possible. The percentages of auxiliaries and dyes were at a minimum level, and this method had
several advantages, such as low-cost materials, low energy costs, no toxic chemicals, no deformation
of the fabric due to low temperature and the possibility of reusing the waste water as a fertiliser.
Therefore, this process can be suggested as an ecological alternative method of dyeing polyester
because it avoids phenolic compounds. Moreover, it can be recommended to the industry due to the
antimicrobial, antioxidant, biodegradability and anti-mutagenic activities of the carriers involved.

Author Contributions: Shahram Radei performed the experimental part and represented the data. Mònica
Ardanuy wrote the first version of the paper and analysed the results. Francisco Javier Carrión-Fité conceived
and designed the experiments. José Maria Canal guided the project.

Conflicts of Interest: The authors declare no conflict of interest.

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