Beruflich Dokumente
Kultur Dokumente
Coloration
dioxide using a nonionic surfactant reverse
Technology
micellar system
K Sawada,a T Takagi,a J H Jun,a M Uedab and D M Lewisc
aDepartment of Chemistry and Material Technology, Kyoto Institute of Technology,
Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
Email: sawada@kk.chem.kit.ac.jp
bDepartment of Design Engineering and Management, Kyoto Institute of Technology,
Society of Dyers and Colourists
Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
cDepartment of Colour Chemistry, University of Leeds, Leeds LS2 9JT, UK
A reverse micellar system in supercritical carbon dioxide has been developed as a dyeing medium.
Water-soluble dyes such as reactive dyes and acid dyes could be sufficiently solubilised in the interior of
a specially constituted reverse micelle. Protein fabrics, silk and wool, were satisfactorily dyed even in
deep shades with conventional acid dyes without any special pretreatment. Cotton cellulose fabric was
also dyed with conventional reactive dyes when the electrostatic force of repulsion between dye and
cotton was eliminated. Compared to previously proposed supercritical dyeing methods, dyeing of
fabrics with this system could be performed at low temperatures and pressures in a short time.
Experimental
Materials SO3Na
The surfactant used in this study was pentaethylene glycol
5
n-octyl ether (C 8E5). C 8E5 was purchased from Nikko
Chemicals Co. Ltd and was used without further purific-
ation. The initial water content of C8E5 was found using NaO3S CH3
the Karl Fisher titration method to be 0.3% w/w. H
1-Pentanol, co-surfactant, was purchased from Nacalai O N
Tesque Co. Ltd and was used after drying with a 3A
molecular sieve. Pure carbon dioxide (> 99.9%) was
purchased from Sumitomo Seika Chemicals Co. Ltd.
Fabrics used in this study were cotton broad cloth, silk O N
H
habutae cloth and wool muslin cloth, which had been
properly desized and scoured with conventional methods. NaO3S CH3
These were purchased from Shikisen-sha Co. Ltd, and were
further pretreated in boiling water for 1 h before use. The 6
dyes used in this study were CI Reactive Red 2 (1), CI
Reactive Blue 74 (2), CI Acid Orange 7 (3), CI Acid Blue 9
(4), CI Acid Red 52 (5) and CI Acid Green 25 (6). All other
Procedures
chemicals used were of reagent grade and were obtained
The high-pressure reaction apparatus was newly
from Kanto Chemical Co. Inc.
constructed in our laboratory. The main component of the
apparatus was a stainless steel viewing cell (4.6 cm3 total
Cl volume) containing a 3 cm diameter optical window, which
was 1.5 cm thick. In all experiments, the prescribed
N N amounts of C8E5 surfactant, co-surfactant, water and dye
H H were loaded into the bottom of the cell before commencing.
N O N N Cl
Liquid carbon dioxide from a cylinder was compressed via
N
a pressurising pump and caused to flow to the reaction cell
until the pressure reached the desired value. The contents
NaO3S SO3Na
of the cell were stirred using a Teflon-coated bar driven
1
by an exterior magnet. Based on the detailed phase diagram
0.8
advance staining of the fabrics due to direct contact with
dye, stirring was not conducted until the temperature and
(c)
pressure reached the chosen operating conditions.
0.4 (d)
Cellulose fibres
10 A similar dyeing process using conventional reactive dyes
and the SC-CO2/reverse micelle medium was applied to
Silk
Wool
cotton fabrics. Unfortunately the dyed cotton fabrics
showed unevenness and only pale shades could be ob-
0 tained. This uneven, pale shade dyeing was not improved
0 4 8 12 16 even under high-pressure or high-temperature conditions
Dyeing time, h
or for prolonged dyeing times. The poor cotton dyeability
Figure 3 Variation of K/S values with time of silk and wool obtained in this study may be explained either in terms
fabrics dye with CI Acid Red 52 from C 8E 5 reverse micellar of low fibre swelling, low concentration of available dye
system (temp., 40 °C; pressure, 16 MPa; w, 5; [C8E5], 62 mM; [1- or lack of affinity between the dye and the fabric.
pentanol], 0.74 M; [Dye], 2% owf)
Dealing with the first issue of insufficient swelling of
fabrics, in contrast to synthetic fibres like polyester, natural
fibres are hardly swollen with SC-CO2. Mishima et al.
emphasised that pretreatment with a swelling agent is
It can be seen that both silk and wool fabrics are indispensable for the dyeing of cotton in SC-CO2 [5]. How-
satisfactorily dyed in deep shades without auxiliaries. In ever considering the successful dyeing of protein fabrics
particular, equilibrium dyeing is completed for silk fabrics described above, natural fibres appeared to be sufficiently
within 15 min even at the moderate temperature used swollen by the water phase in the reverse micelle system
(40 °C). Acid dye solubilised in the water pool would for adequate dye penetration to occur.
effectively migrate into the fibre due to the high dis- The second factor to be considered is an insufficient
persibility and mass transfer rate of SC-CO2. On the other concentration of dye in the system. As reported previously,
hand, the dyeing rate of the wool fabric dyed under the we have found that cotton fabrics are satisfactorily dyed
same conditions is lower than that of silk, although the in deep shades with direct dyes and reactive dyes from
final colour depths of the dyed wool and silk fabrics are ionic reverse micellar systems in organic solvent [8].
similar. These differences in dyeing rate may be attribu- Because of the success of the previous study, the dyeing
table to the characteristic structure of the wool fibre. In conditions (such as the concentration of dye, liquor ratio
contrast to the silk fibre, the surface of the wool fibre is and water content) in this study were adjusted to be almost
covered with highly hydrophobic cuticle cells. In the the same as the previous work, with the exception that the
conventional water-based dyeing process, the dyeing of hydrophobic component of the reverse micelle system was
wool is performed at a high temperature (98 °C). Under SC-CO2. Since complete solubilisation of the dye in the
these conditions the hot water swells the non-keratinous system occurred, we can conclude that the solubility of the
proteins of the cell membrane complex between the cuticle dye is not the cause of the uneven dyeing.
and cortical cells and also the non-keratinous endocuticle, The third suggestion was that the poor quality dyeings
moving them apart and allowing access for the aqueous dye were the result of a reduction in the affinity between the
solution into the bulk of the fibre. Dyeing at low dye and the fabric in the SC-CO2/reverse micelle medium.
temperatures (e.g. 40 °C) with a small amount of water may
not have sufficient effect on the cuticle cells to achieve 30
access to the fibre. Consequently, migration of dye into the
fibres would be restricted to the surfaces of the wool fibre.
Figure 4 shows the dyeability of silk fabrics as a
function of working pressure. Similar results were also 20
obtained for wool fabrics when dyeings were performed
for more than 1 h.
K/S