Enzyme applications in the textile industry
Nelson Durán and Marcela Durán
INTRODUCTION
Developments and advances in the processing of cotton
fabrics to minimise the environmental effects of
processing effluents are reviewed. Many different
approaches have been taken to the preparation, dyeing
and finishing of cotton using enzymes. Physical methods
focus on surface modification by exposure to high-energy
sources and the use of ultrasound to facilitate wet pro-
cessing. This review concentrates on biological methods
such as the replacement of stone-washing of denim
garments with cellulases, and other enzymatic related
processes [1–6].
CELLULASES
Cellulases are well established in textile wet processing as
agents for fibre surface modification [7–9]. Cellulase
enzymes are being used more and more in denim
washing to achieve a stone-washed look without the need
for stones, or at least fewer of them. The use of the
enzymes on cotton provides a softer finish and a different
surface appearance [10]. Cellulase has various effects on
man-made cellulosic fabrics such as lyocell (Tencel),
viscose and cellulose acetate. On both viscose and lyocell,
cellulase alters the handle and drapeability, and removes
surface fuzz. Cellulase also reduces the tendency of
viscose to pill and reduces fibrillation of lyocell, but on
cellulose acetate the effects tend to be less marked [11].
Cellulase pretreatment has been found to result in an
increase in the uptake of the natural dyes chlorophyll and
carmine, and did not affect fastness properties [12]. The
best known applications are the ageing of fabric surfaces,
to achieve the stone-washed look of denim garments, and
also the cleaning and renewing of fabric surfaces that are
damaged with microfibrils, fuzz and loose fibres. The
different effects can be obtained with different enzyme
composition: endoglucanase (EG) or EG-rich preparations
are best for ageing and defibrillation of fibre surface, while
complete cellulase systems are best for cleaning and
depilling effects [13–16]. The finishing effects delivered by
cellulases are always obtained in processes in which
strong mechanical agitation of the fabric is provided
during the treatment by, for example, rotating-drum
washers and jets [9]. The existence of a synergistic affect
between EG activity and higher levels of mechanical
agitation has also been identified [5,17–20].
The mechanical action provided during the processing
of cotton with cellulases seems to be a key issue in
understanding the treatment mechanisms involved. It
had been suggested that prior mechanical agitation makes
the cellulose chain more accessible for cellulase hydrolysis
[21]. More recently cotton fabrics were treated with
cellulase mixtures of different compositions, and then
washed in a process involving mechanical agitation. The
fibre surface did not change significantly after cellulase
treatment, but after washing the properties of the surface
were different, depending of the enzyme quality used
(endoglucanase- or cellobiohydrolase-rich preparation)
[20].
In recent years biofinishing, an application technique
using enzymes such as cellulase and proteases to digest
protruding fibres, has gained considerable attention.
Several studies have reported that a certain weight loss is
desirable as a result of an effective enzyme treatment. In a
recent study the relationship between weight loss and the
amount of glucose and amino acids released was
examined. Apparently a relationship exists between these
parameters, confirming the efficient activity of the
cellulase and protease in the biofinishing [22]. Cotton and
wool fabrics have been treated with a low-temperature
oxygen plasma or cellulase, or both, and examined for
their mechanical and dyeing properties. Plasma-treated
cotton showed reduced strength, while the rate of weight
loss in subsequent cellulase treatment decreased com-
pared with that of untreated cotton. This study showed
that the plasma attacks the surface of the fibre, and the
cellulase affects mainly the inner part of the fibre [23].
Linen, cotton and viscose knits have been treated with
the cellulase enzyme Cellosoft L, which resulted in
improved appearance and handle [24]. The action of a
recombinant cellulase, endoglucanase V from the fungus
Humicola insolens, has been followed by scanning electron
microscopy (SEM) in classical longitudinal views as well as
in cross-sections of cotton fibres. Endoglucanase V
appears to restrict its action to the hydrolysis of the loose
fibrils created at the surface of the fibres, and no indication
of extensive enzyme penetration and damage to the
interior of the fibres could be detected by SEM. The
adsorption sites for endoglucanase V on cotton fibres were
examined by transmission electron microscopy (TEM) on
ultra-thin cross-sections after immune-gold labelling of
the enzyme. This approached showed that the enzymes
did not penetrate the fibres but remained at their surface.
The use of an immune-gold labelled cellulase provides a
new way to characterise the surface features of the cotton
fibres [25,26].
Several cellulosic fabrics were treated with a whole
cellulase, a mixture of exo- and endo-activities and a
cellulase enriched for a particular type of endoglucanase
REV. PROG. COLORATION VOLUME 30 2000 41
activity. Linen was the most susceptible to enzymatic
hydrolysis, followed by viscose fibre, cotton and lyocell.
Whole cellulase exhibited higher efficacy than the endo-
enriched cellulase with respect to surface fuzz removal.
The endo-enriched cellulase was less aggressive than the
whole cellulase and resulted in less fabric damage. The
whole cellulase was best for treatment of cotton and
lyocell fabrics and the endo-enriched cellulase was more
suitable for linen, viscose and delicate cotton knits [27,28].
Three methods were evaluated for removing fibres
protruding from the surface on 100% cotton knit fabrics, to
improve their quality at the point of purchase and to
maintain quality during the life of the garment. Singeing
fabric either in the greige state or after batchwise dyeing in
a soft-flow jet was the first method evaluated.
Biopolishing using cellulase was used to determine the
effect of enzyme treatment before and after dyeing. The
third method was home laundering the fabrics, using a
detergent containing a cellulase; the process was
evaluated after every five cycles (up to 30 in total),
following by tumble drying. It was demonstrated that
whenever surface fibres can be removed, by any method,
or protected from excessive abrasion during processing,
fabrics will maintain a better surface appearance after
multiple laundering [29]. The action of cellulase enzymatic
pretreatment in the alkaline scouring of cotton fabrics was
studied. Improved removal of seed-coat fragments was
the primary goal of the experiments, and spinning
blowroom waste, rich in seed-coat fragments, was the
main target substrate for enzymatic studies. Commercial
cellulases, hemicellulases and pectinases were used. The
presence of enzymes enhanced penetration of the alkaline
scouring solution and increased the alkaline degradation
of seed-coat fragments, to an extent that depended on
time and enzyme concentration; 28–34% of the untreated
seed-coat fragments were solubilised by cellulase. With
consecutive cellulase treatment and traditional pad–steam
scouring, weight loss was as high as 78–86%, compared
with the alkaline cotton scouring (control), which resulted
in only 66% weight loss [30].
Cavaco-Paulo and co-workers have characterised the
activities of total cellulase, and EG-rich and CBH-rich
cellulases from Trichoderma reesei, and have shown that
their activities towards cotton fabrics are influenced by
ionic strength and adsorbed ionic species as well as by
temperature and pH [31,32]. Adsorption and kinetic
experiments confirmed that increasing mechanical
agitation favors EG attack by greatly increasing the
availability of sites for EG adsorption. It was not clear
whether this was a consequence of fibre fibrillation
damage or of improved access to fibre surfaces deep
within the fabric structure [5].
A combination of pectinase and cellulase significantly
improves water wetting and retention properties, to a
level similar to those of commercially scoured cotton
fabrics [33]. Treatment with cellulase and protease not only
results in removal of impurities but also improves the
wettability of the fabric. Enzyme-treated fabrics have a
42 REV. PROG. COLORATION VOLUME 30 2000
softer handle. Treatment conditions have been optimised
with respect to concentration and temperature of the
enzymes [34–36].
Work has also been carried out on cellulases used in
conjunction with proteases [37,38] and pectinase [39].
Other experimental treatments have included: cellulase
with ultrasound [40], commercially available cellulases
[41–43], alkaline cellulase [44] and cellulase with abrasives
[45]. Heat-stable glycosidase enzymes and the corres-
ponding genes derived from various Thermococcus,
Staphylothermus and Pirococcus organisms have been
disclosed and can be utilised in the textile industry [46]. A
cellulase preparation with high activity in endoglucanase
(more than 15% of total cellulase activity) that can be used
in the finishing of cellulose-containing textiles has been
described. Use of these components in finishing gave
improved biofinishing or a stone-washing effect, and
there was improved colour properties, improved visual
appearance and a lower tendency to pilling. The strength
properties of the textile materials were essentially
unchanged when compared with those of previously
used cellulase components [47].
XYLANASES
The xylanolytic system of Aspergillus versicolor is controlled
by induction and carbon catabolic repression. Cellulase-
free xylanase can be also utilised for preparation of
cellulose pulps and in the preparation of textile fibres [48].
A combined treatment of pectinase and xylanases with
reduced amounts of cellulases was equally effective as
using high levels of cellulases in the removal of protruding
superficial fibres. The resulting fabric surface was
smoother after enzyme-treated samples compared with
the untreated control; mixtures of enzymes were more
effective than cellulase treatment alone [49].
An extract isolated from the fungus Penicillium
janthinellum, which produces large amounts of xylanase
with no detectable cellulase activity, was used as a model
system to study enzyme induction and production, and to
illustrate the use of such a preparation in the recovery of
cellulosic textile fibres [50].
LIPASES
Before cotton fabrics can be dyed and finished, manu-
factured and natural impurities (dirt, wax, pectin, protein
and hemicellulose) must be removed. Woven fabrics
contain residues of products used for machine lubrication.
If not properly removed, these impurities can result in
problems occurring during dyeing and finishing [51].
The ability of six lipases to improve the hydrophilicity
of several polyester fabrics was studied. Five of them
improved the wetting and absorbency properties of
regular polyester fabrics more than did alkaline hydrolysis
under optimal conditions. Compared with aqueous
hydrolysis, the enzyme reactions were highly effective
under more moderate conditions, including a relatively
low concentration, a shorter reaction time, a lower
ambient temperature and no buffer. Improved wettability
was accompanied by full strength retention compared
with the significantly reduced strength and mass
following alkaline hydrolysis. The wetting and
absorbency properties of sulphonated polyester and
microfibre polyester fabrics were also improved by lipase
[52–54].
LACCASE AND OTHER OXYGENASES
The scope for oxidative processes in bleaching cotton
fabric has been investigated. Neither the enzymatically
catalysed activation of hydrogen peroxide by the use of
peroxidase nor activation by the use of laccase proved to
be suitable for bleaching. However, the use of glucose
oxidase coupled with desizing by glucoamylase effected a
significant improvement in brightness values, with the
added benefit of conferring a soft handle. When this
process was compared with an alkaline hydrogen
peroxide process, the advantages of the enzymatic process
included minimisation of wastewater pollution loads and
reduction in chemical consumption [55]. Important
advances in the use of recombinant α-amylase in textile
desizing, starch liquefaction and washing have been
described [56].
One new process consists of treating the substrate in an
aqueous dye liquor with a dye system that contains
polycyclic aromatic compound (e.g. p-phenylenediamine).
The system also includes a hydrogen peroxide source and
at least one enzyme exhibiting peroxidase activity and/or
at least one enzyme exhibiting oxidase activity (e.g
laccase), plus one or more aromatic compounds. A dyed
denim sample treated with p-phenylenediamine showed
deep purple/brown on blue and white yarns before
washing. After washing the shade was lighter on the
white yarns [57–60].
PROTEASE
Carefully controlled treatments with proteolytic enzymes
were used to reduce the buckling load and collapse
energy of wool yarns. These treatments were shown to
improve the softness and reduce the subjectively per-
ceived harshness of fabrics knitted from treated yarns [61].
Wash-fast wool materials were prepared by treating
mechanically spun, partially oxidised wool fibre yarns
with a protein-degrading enzyme (Savinase) [62]. Details
of a protease enzyme for use in foam detergent for textile
cleaning were recently published [63]. A comparative
study of dyeing properties of two natural yellow pigments
on cotton and wool fibres has been published. The
enzymes used were α-amylase, amyloglycosidase and
trypsin. The wash and light fastness properties of all dyed
samples were studied [64].
CATALASE
The use of peroxide-decomposing enzymes during
washing after the pretreatment of cotton was recently
examined. Amongst the benefits listed were a shorter
washing process, savings in water consumption, reduced
pollution, and an increase in the efficiency and repro-
ducibility of subsequent dyeings [65]. The application of
native catalase in discontinuous washing processes
enables quick and complete decomposition of remaining
peroxide. Immobilised catalase was more stable against
fluctuations in temperature, pH and the presence of
surfactants. The application of immobilised catalases in
washing systems showed a reduction in peroxide content
and water costs in simulations, compared with figures
obtained from common washing processes [66].
ENVIRONMENTAL FACTORS
Environmental protection is becoming a serious concern
for textile wet processors, and in the dyeing and finishing
industry the pretreatment of cotton can cause environ-
mental problems. In the desizing process, yeasts have
been introduced into the enzyme system by different
application methods to decrease the chemical oxygen
demand loading of the effluents [67]. Decolorisation of an
artificial textile effluent and its component dyes in the
presence of primary carbon and an energy source was
examined. The relationship between decolorisation and
various ligninolytic enzymes was elucidated [68]. In two
other recent papers several biotechnological issues have
been discussed [69,70].
Many studies on the treatment of textile effluents with
enzymes and fungi have been published [71–81]. A recent
paper examined the action of phenoloxidase-like activities
of siderophores on dyes and textile effluents [82].
* * *
The authors would like to acknowledge support from
FAPESP, PRONEX and CNPq.
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Nelson Durán is with the Instituto de Química, Universidade
Estadual de Campinas, Sao Paulo, Brazil; Marcela Durán is
with the Food Science Faculty, Department of Food Tech-
nology, Universidade Estadual de Campinas, Sao Paulo,
Brazil.