76 Color. Technol.

, 121 (2005) Web ref: 20050205

Coloration
Technology
Society of Dyers and Colourists
Dyeing of polyester using micro-
encapsulated disperse dyes in the
absence of auxiliaries
Zhong Yi,* Feng Jihong and Chen Shuilin
College of Chemistry and Chemical Engineering, Donghua University, Shanghai 200051,
China
Email: zhongyi@mail.dhu.edu.cn
Received: 20 September 2004; Accepted: 6 January 2005
Polyurea microcapsules were prepared in this study, using disperse dye as the core material and
diphenylmethane-4,4-diisocyanate as the wall-former. Microencapsulated disperse dyes have
been characterised in terms of their thermal properties, average particle size and size distribution,
morphological structure and composition. Polyester fabric was dyed with microencapsulated CI
Disperse Blue 56 using a high temperature dyeing process without dispersing agents, penetrating
agents, levelling agents or other auxiliaries. The quality of the polyester fabric dyed in this manner
without reduction clearing was at least as good as that dyed traditionally after washing and reduction
clearing. After separating off the polyurea microcapsules, the dyebath was virtually colourless and was
shown to be suitable for reuse.
Introduction
Water is a valuable raw material and has limited
availability. The dyeing of textiles has traditionally relied
on water as the solvent for dyestuffs. In the case of polyester
(PET) fabrics, for example, these are dyed under aqueous
conditions using disperse dyes, with chemical auxiliaries,
such as dispersing agents, penetrating agents and levelling
agents, in the dyebath. Unfortunately, residual auxiliaries
and dyestuff may be present in the efuent and may cause
pollution. The efuent can be decolorised by destroying
the dyestuff. This, however, does not eliminate pollution
and can also give problems with sludge disposal. The
wastewater problem has become one of the most pressing
issues in textile dyeing [1].
In order to avoid such environmental factors, alternative
dyeing processes have been developed which restrict
or avoid the use of water. Examples include dyeing in
supercritical carbon dioxide (SC-CO
2
), thermal transfer
printing, solvent dyeing, pigment dyeing and ink-jet
printing, all of which offer an innovative approach to
textile dyeing and printing. The SC-CO
2
technique was
developed to avoid the use of water entirely, but has the
drawbacks of high initial cost and limitations in the choice
of dyestuff [1].
Microcapsules, on the other hand, offer the advantages
that they are adaptable, the active substance can be released
at a controlled rate and the carrier is essentially non-toxic
[2,3]. Microencapsulated dyes have attracted interest in the
textile area. By careful selection of dyes, phase transition
materials and auxiliaries, special coloured effects can be
obtained. Disperse dyes are ideal for microencapsulation
and were rst offered in Japan in the 1970s by Matsui
Shikiso Chemcial Co. Ltd [4]. Hayashi Chemical later
developed microencapsulated reactive, acid and basic dyes,
which could be printed to create snow-like coloured ecked
effects [5]. Sawanoi developed magnetic microencapsulated
disperse dyes which were able to dye PET fabrics by a
thermosol process using special dyeing machinery [6].
Chen et al. have also produced melamine and polyurea
microcapsules containing disperse dyes for both thermosol
and high temperature dyeing [7].
The present investigation has led to a novel method
of dyeing PET fabric in the absence of auxiliaries using
disperse dyes microencapsulated with polyurea. Since
no auxiliaries are involved, the spent dyebath can be
recovered and reused. In this study, differential scanning
calorimetry (DSC), scanning electron microscopy (SEM)
and particle size analysis were used to obtain information
about the character of the microencapsulated disperse
dyes, as well as their dyeing performance on PET fabric. A
comparison has been made between the use of distilled and
recovered water.
Experimental
Materials
PET fabric (70 g/m
2
, plain weave, warp and weft 100 d) was
supplied by the Wujiang Textile Co. (China).
Diphenylmethane-4,4-diisocyanate (MDI) was obtained
from Shanghai Reagent Co. and, after drying in a vacuum
oven for 3 h, was used for the wall material. Emulsier
GPE2040 was provided by Gaoqiao Fine Chemicals Co. Ltd
(China) and the protective poly(vinyl alcohol) colloid PVA
1799 by Fanjie Chemicals (China). The anionic dispersing
agent NNO (polyoxyethylene octanol) and the nonionic
penetrating agent JFC (sodium bisnaphthalenesulphonate)
were provided by Gaoqiao Fine Chemicals Co. Ltd (China).
All the chemicals used in the study were of reagent grade.
CI Disperse Blue 56 (1) and CI Disperse Red 60 (2) were
obtained from Hangzhou Jihua Chemical Co. (China).
20050205_j112-04.indd 1 23/03/2005 11:03:22
Color. Technol., 121 (2005) 77 Web ref: 20050205
Preparation of microcapsules
Polyurea microcapsules (PMs) were prepared using an
interfacial polymerisation reaction in emulsion form as
described in previous studies [8,9]. PMs contained MDI
(wall material) and disperse dye (core material) and were
prepared at an adequate ratio with GPE2040 (2% w/w) as
the emulsier and PVA (1% w/w) as the stabiliser. A similar
procedure was used for the incorporation of disperse dyes
in PMs, the reaction being carried out at 50 C for 180
min. Distilled water was added to the slurry to keep the
microcapsules in a monodispersed condition (water-to-slurry
ratio, 7:93). After gently stirring the slurry until it reached
room temperature, the microcapsules were separated by
decantation. After washing with 10% w/w ethanol to remove
unreacted isocyanate, the microencapsulated material was
dried in a vacuum oven at 25 C for 24 h.
Characterisation of the microcapsule
A di f ferential scanni ng calori meter, Model 822e
(Mettler Toledo, Switzerland), was used for DSC and the
thermogravimetric (TG) analysis was carried out using a
Model TGA 7 instrument (Perkin-Elmer, USA). Samples
(ca. 5 mg) were heated at a rate of 10 C/min to 330 C under
constant nitrogen ow.
SEM was performed on a JSM-5600LV electron
microscope (Jeol, Japan). The microcapsules were sprinkled
on to a sample plate and sputter-coated with gold for
examination.
Mean particle size and size distribution were determined
using an LS 13320 particle size analyser (Beckman Coulter,
USA). The test was carried out using a few drops of
suspension following 10 min of dispersion by a sonicator.
Spectrophotometric assessment was conducted on a
752N UVvis spectrophotometer (Lengguang, China) at the
wavelength of maximum absorption of the dye (
max
).
Loading content
The dry PM powder was examined to ascertain the
quantity of dye contained. The microcapsules (32.0 mg)
were dissolved in 100 ml acetone at room temperature and
the dye concentration determined by spectrophotometer
using a calibration curve of absorption at
max
[dye 1: 630
nm (acetone); dye 2: 516 nm (acetone)].
Dyeing and measurements
Dyeing process
PET fabrics were dyed in a Roaches 656/85 high temperature
machine (Roaches Engineering Ltd, UK) at a liquor-to-goods
ratio of 50:1 using distilled and recovered water, respectively.
In order to achieve a comparable depth of colour, the dyebath
comprised 80 ml water plus either 0.224 or 0.083 g of the PM
based on 1 or 2, respectively. For the control experiments,
using the dyes themselves, 0.032 g of 1 or 0.038 g of 2 was
used, plus dispersing agent (NNO, 2 g/l) and penetrating
OH
NH
2
O
O NH
2
OH
Br
1
O
O NH
2
OH
2
O
agent (JFC, 1 ml/l). After adjusting to pH 4.5, PET fabric
(1.6 g) was immersed in the dyebath and the temperature
was raised to 130 C at a rate of 1 C/min. Dyeing was
continued at this temperature for 60 min, after which time
the temperature was lowered to 50 C at 3 C/min. The dyed
fabrics were then washed in water, and those dyed using
traditional disperse dyes were further cleared using soap
and reducing liquor in turn.
Dye uptake
CIELAB and colour yield (K/S) values were measured using
a Datacolor SF600 instrument at
max
using illuminant D65
and 10 observer. After Soxhlet extraction of the dye with
xylene, the dye concentration absorbed on the fabric was
measured on the 752N UVvis spectrophotometer at
max

[dye 1: 626 nm (xylene); dye 2: 514 nm (xylene)].
Levelness and fastness testing
Levelness was measured according to ISO 105/J01-1987.
Fastness to washing and rubbing were determined using
ISO/DIS 105-C03:1989 and ISO 105X-12:1993.
Analysis of dye wastewater
The residual dyebaths were filtered and assessed for
chemical (COD) and biological oxygen demand (BOD) [10].
The absorbency at
max
was determined using a Pharmacia
LKB Novaspec Model II colorimeter. The absorbency at

max
was compared with that from the untreated disperse
dyes using a UV-3000 dual-wavelength double-beam
spectrophotometer (Shimadzu, Japan).
Results and Discussion
Thermal properties of the PMs
DSC and TG results are given in Figure 1 and show the
thermal properties of PMs containing dye 1. The DSC
results provided data about polymer properties such as
change in melting temperature and heat capacity. In the
DSC analysis, thermal change was not apparent below
280 C, with an absorption peak around that temperature
(Figure 1a). Between 160 and 230 C the curve was more
uniform, and endothermic transition of the dyes was not
detected. This may be attributed to the controlled release
provided by the microcapsule wall, and the fact that
endothermic transition of the dye was partially offset by the
exothermic transition of the polyurea. This is a feature of
the thermosetting properties of the PM, and indicated that
a durable microcapsule had been successfully formed.
TG analysis supported the results given by DSC thermal
analysis and showed that the microcapsule weight
decreased with increasing temperature by as much as 40%
(Figure 1b). A small initial weight loss occurred between
160 and 230 C due to progressive release of core material
from the microcapsule. A shoulder occurred above this
temperature, following which the bulk of the weight loss
took place. According to the TG result, the core volume in
the PM was ca. 15% as the initial weight loss went from 97
to 82% on the vertical axis.
Particle size and size distribution
It was found that the particle size distribution of the PMs
containing disperse dyes followed a normal distribution.
20050205_j112-04.indd 2 23/03/2005 11:03:30
78 Color. Technol., 121 (2005) Web ref: 20050205
0 4
40 80 120 160 200 240 280 320
8 12 16 20 24 28
Temp, C
Time, min
(a)
40 100 150 200 250 300 350
0
20
40
60
80
100
Temperature, C
W
e
i
g
h
t

l
o
s
s
,

%
(b)
Figure 1 (a) DSC and (b) TG for PMs with dye 1
The mean size of all the resulting particles after
emulsication stirring at 10 000 rpm was about 23 m,
and the size distribution was narrow (ca. 660 m).
Morphological structure of microcapsules
SEM photographs of the surface of the PMs prepared
using MDI and dye 1 are shown in Figure 2. The surface
of the microcapsules were rough and full of micropores,
presumably due to the action of the emulsion globules
containing MDI monomers continuously diffusing from
the interior of the microcapsule. It could be assumed from
their surface morphology that polyurea microcapsules are
well suited to the protection and sustained release of core
materials. Moreover, the microcapsules behaved as heat-
resistant containers with good thermal properties.
Loading content
Generally, the content of disperse dye in the microcapsule
using a similar processing procedure was about the same.
The content of dye 1 in the PM was 13.8% at an initial core-
to-wall ratio of 1:3, a conclusion supported by TG thermal
analysis.
Dyeing behaviour
Under high temperature dyeing conditions water has lower
surface tension and is better able to penetrate the wall of
the PM cell. It then dissolves the dye to form a saturated
Figure 2 SEM photographs of dye 1 in PM form: (a) 2000; (b)
5000; (c) 20 000
solution. Since there is a disparity in dye concentration
between the inside and outside of the PM, dye molecules
diffuse from the cell and, simultaneously, water molecules
enter it until equilibrium is reached. When PET fabric is
present in the dyebath, dye molecules are adsorbed on
to it and diffuse into the bre to bring about dyeing. The
balance of dye in the bath is then disturbed, and further
solution and diffusion of dyes from the PM continues.
The dissolutiondiffusionadsorptionuptake process
continues until the required shade is obtained.
On the other hand, in the conventional dyeing process
the dyebath contains dye in three states, namely solid dye,
20050205_j112-04.indd 3 23/03/2005 11:03:31
Color. Technol., 121 (2005) 79 Web ref: 20050205
dissolved dye and dye in micelles, and the equilibrium may
be expressed as follows (Eqn 1).
Dye Dye Dye
solid in micelle dissolved
(1)
Removal of dissolved dye by the bre results in more
passing into solution. The dye in the micelles may therefore
be considered to act as a reservoir [11], and then goes
through a solubilisationdissolutionuptake process to
give the required shade.
The dyeing behaviour of the dyes in PM form was
compared with fabric dyed traditionally (Table 1). The
results show that the levelness and fastness to soaping and
rubbing of PET samples dyed with 1 in PM form, without
auxiliaries or reduction clearing, were at least as good as
those obtained by traditional disperse dyeing after washing
and reduction clearing.
The excellent wash-off properties of the PET fabric dyed
with the PM disperse dyes may be attributed to reduced
staining of the surface of the bre, making the need for
washing much less important. On the other hand, the
fabric dyed conventionally with disperse dyes had much
greater surface staining due to the solubilisation of dye in
the presence of surfactant, making thorough washing and
reduction clearing necessary.
The fastness properties of the fabrics dyed using this
novel level dyeing method will be further evaluated in a
later study.
Dyebath wastewater
After the completion of dyeing, residual spent PMs in
the bath may be removed by deposition or ltration. The
absorbency of the wastewater and the content of COD
and BOD pollutants after different dyeing processes are
shown in Table 2. The wastewater after dyeing with PMs
was recovered by ltration and was almost colourless,
whereas that from the traditional dyeing process was dark
blue. It was also striking that using dye in the form of a
PM dramatically reduced the COD and BOD pollutants in
the efuent.
Table 2 Properties of the wastewater
Dye COD BOD Appearance Absorbance
a
1 1.45 10
3
971 Dark blue 0.86
1/MDI
b
50 14.7 Colourless 0.02
a At 600 nm
b After ltration
Reuse of recovered wastewater
To assess the practicability of reusing the recovered
wastewater, PET fabric samples were dyed under similar
conditions using dyes 1 and 2 in PM form in filtered
wastewater (from the microencapsulated dye 1 dyebath)
and in distilled water. The dyeing rate curves are shown
in Figure 3. In each case the dyeing rate curves are
similar, which means that residual dye 1 remaining in the
wastewater had little inuence on the dyeing behaviour of
this dye in PM form. To conrm this, the K/S values and
colour differences on PET fabric dyed in the two media
were determined.
The K/S values and colour differences between dyeing in
distilled water and ltered wastewater are shown in Figure
4 and Table 3. The K/S value of fabric dyed in wastewater is
very close to that of the fabric dyed in distilled water, and
the chroma difference (C*), hue difference (H*) and total
50 100 150 200 250 300 0
0
50
100
Time, min
D
y
e

u
p
t
a
k
e
,

%
(a)
Distilled water
Filtered wastewater
50 100 150 0
Time, min
0
50
100
D
y
e

u
p
t
a
k
e
,

%
(b)
Distilled water
Filtered wastewater
Figure 3 Dyeing rate curves of PM based on (a) 1 and (b) 2
Table 1 Fastness properties of PET dyed traditionally with dye 1 (2.0% owf)
a
and with dye 1/MDI
Rub fastness Wash fastness (60 C) Wash fastness (95 C)
Fading of Staining Fading of Staining
Staining Staining original (undyed Staining original (undyed Staining
Dye K/S Levelness (dry) (wet) sample PET) (cotton) sample PET) (cotton)
1 19.85 45 5 5 45 45 5 45 2 3
1/MDI 19.98 5 5 45 5 5 5 45 4 45
a Dyed with a high temperature method
20050205_j112-04.indd 4 23/03/2005 11:03:32
80 Color. Technol., 121 (2005) Web ref: 20050205
400 500 600 700
5
10
15
, nm
K
/
S
(b)
Distilled
water
Filtered
wastewater
Figure 4 K/S curves of PET fabric dyed with (a) 1 and (b) 2
Table 3 Comparison of fabrics dyed with microencapsulated dyes in distilled water and in reused dyebath after ltration
Dye Medium K/S L* a* b* C* H* E*
1/MDI Distilled water 19.98
Reused dyebath 20.15 0.114 0.221 0.169 0.224 0.165 0.301
2/MDI Distilled water 16.85
Reused dyebath 16.31 0.825 1.050 0.444 1.112 0.253 1.408
colour difference (E*) are acceptable in the case of dye 1
and small in the case of dye 2.
Conclusions
Dye 1 was prepared in PM form and its thermal properties,
particle size and size distribution, morphology and
composition were investigated. The microencapsulated dye
was found to have a narrow size distribution and a surface
comprising large numbers of micropores.
When PET was dyed using microencapsulated dye 1 at
high temperature in the absence of auxiliaries, and without
reduction clearing, levelness was improved and fastness to
washing and rubbing on PET fabric were at least as good
as by dyeing traditionally with reduction clearing. The
wastewater recovered by ltration was virtually colourless,
whereas that from traditional dyeing was strongly coloured.
Values for COD and BOD of dyebaths from dyeing with
dye in PM form were lower than those values for spent
dyebaths containing non-PM material. There was virtually
no difference in dyeing performance using recovered or
distilled water.
References
1. A Q Hou and J J Dai, Proc. 83rd TIWC, 2 (2004) 663.
2. R Arshady, Polym. Eng. Sci., 30 (1990) 915.
3. R Arshady, Polym. Eng. Sci., 33 (1993) 865.
4. G Kemo, Jpn Text. News, 4 (1974) 40.
5. Text. Manufacturer, 102 (1975) 32.
6. Y Sawanoi and T Hori, Seni Gakkaishi, 58 (2002) 68.
7. Chen Shuilin and Li Zhuo, CN1443807A (University of
Donghua; 2003).
8. Li Zhuo and Chen Shuilin, Int. J. Polym. Mater., 53 (2004) 385.
9. Li Zhuo, Chen Shuilin and Zhou Shizhou, Int. J. Polym.
Mater., 53 (2004) 21.
10. Standard Met hods for t he Examination of Water and
Wastewater, 17th Edn (Washington: American Public Health
Association, 1989).
11. R H Peters, Textile Chemistry, Vol III The Physical Chemistry
of Dyeing (Amsterdam: Elsevier, 1975) 76.
400 500 600 700
5
10
15
20
, nm
K
/
S
(a)
Distilled water
Filtered wastewater
20050205_j112-04.indd 5 23/03/2005 11:03:33