Progress in Organic Coatings 85 (2015) 221–229

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Antimicrobial and insect-resist wool fabrics by coating with

microencapsulated antimicrobial and insect-resist agents
Mohammad Mahbubul Hassan ∗ , Matthew Sunderland
Textile Science and Technology Team, Food and Bio-based Products Group, AgResearch Limited, Private Bag 4749, Lincoln, Christchurch 8140, New Zealand

a r t i c l e i n f o a b s t r a c t

Article history: In this work, various types of antimicrobial and insect-resist agents were microencapsulated by several
Received 13 November 2014 techniques to minimise their toxicity to humans. The microencapsulated antimicrobial and insect-
Received in revised form 7 April 2015 resist agents were applied to wool fabrics by a pad-dry-bake method, and their performance was
Accepted 18 April 2015
assessed in accordance with standard methods. The durability of the treatments to ageing and wash-
Available online 15 May 2015
ing was evaluated. It was found that the antimicrobial and insect resist agents migrated to the outer
surface of the capsules during ageing. Of the antimicrobial agents investigated, poly(N,N-dimethyl-2-
Keywords:
hydroxypropylammonium) chloride or Barquat PQ 2 encapsulated with polylactic acid showed the best
Microencapsulation
Wool fabric overall antibacterial performance after 10 cycles of International Wool Secretariat (IWS) 7A washing and
Coating also after ageing. The clothianidin insecticide encapsulated with polylactic acid showed the best insect-
Antimicrobial resist performance according to Wools of New Zealand Test Method 25 at a level of 50 ppm, passing
Insect-resist this test method even after 10 cycles of washing. The washed fabric showed 85% insect mortality and
Durability the mean wool mass loss was only 4.6 mg. The fabric handle properties were only slightly affected by
the treatments. The developed methods may find application in industry as they are quite durable to
washing.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Previous studies showed that consumers want to have various
functionalities in their apparel, and that one of the key attributes
they wanted is antibacterial activity [1–4]. This was not surpris-
ing as modern consumers are increasingly concerned about health
and wellbeing [5]. Wool textiles generally do not allow bacteria to
adhere to their surface, but in contact with the human body offer a
favourable environment for bacterial growth [6]. Microbes present
in the fabric can not only affect the health and wellbeing of the
wearer, but some species can create unpleasant smells and can
even degrade fabric materials. Various antibacterial agents, such
as quaternary ammonium compounds, hexamethylene biguanide
hydrochloride, and triclosan have been investigated for making
textile products antibacterial [7–10].
Another antimicrobial agent is silver, which is a broad spectrum
antimicrobial agent with a long history in the treatment of burns.
While metallic silver is relatively inactive, silver ions are effective
against a wide range of bacteria [11]. Silver compounds produce
their antimicrobial effect by the time-dependent release of silver
∗ Corresponding author. Tel.: +64 3 321 8755; fax: +64 3 321 8811.
E-mail address: mahbubul.hassan@agresearch.co.nz (M.M. Hassan).
ions and their clinical efficiency is directly related to the constant
presence of free silver ions in the local microbial environment [12].
Recent advances in nanotechnology have led to the introduction of
fabrics treated with silver nanoparticles, and such fabrics have been
widely embraced by sportswear manufacturers, although environ-
mentalists and toxicologists have raised concerns about the effects
on the aqueous environment and human health of silver leached
from such fabrics during wear and washing [13,14]. In addition to
toxicity of silver nanoparticles, the binding of silver nanoparticles
to the surface of fibres, particularly wool, is problematic. Therefore
alternatives to silver are needed.
Quaternary ammonium compounds are proven antimicrobial
agents and have been investigated [15,16] for use on wool to
impart antibacterial functionality. However, the quaternary ammo-
nium compounds slowly wash away during laundering, resulting
in a considerable loss of antimicrobial activity. Zhu and Sun
applied three quaternary ammonium compounds, cetylpyridinium
chloride, cetyltrimethylammonium bromide and benzyldimethyl-
hexadecylammonium chloride to wool but found that after 10
washings the percentage of Escherichia coli mortality dropped from
99.3%, 100% and 97.3% to 79.3%, 10.3% and 0% respectively [16]. As
all quaternary ammonium compounds and triclosan are relatively
toxic, their contact with the human body at high concentrations
could be harmful. Encapsulation of antibacterial agents would be an

http://dx.doi.org/10.1016/j.porgcoat.2015.04.016
0300-9440/© 2015 Elsevier B.V. All rights reserved.
222 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229
ideal method to overcome this problem as the antibacterial agents
would be inside the capsules and their release will be controlled,
substantially diminishing the chance of a damaging effect on skin.
Micro-encapsulated copper oxide and herbal extracts have been
investigated for textile applications [17]. Encapsulation also allows
the use of antibacterial agents that are highly water-soluble that
would otherwise leach out quickly from fabric during washing and
sweating.
Wool products can be eaten and digested by larvae of partic-
ular insects, such as the common clothes moth Tineola bisselliella.
Not only are the aesthetic properties of wool apparel attacked by
moths compromised, but the damage may be extensive enough to
render the product unusable. To protect wool apparel from insect
damage, they are sometimes treated with insect-resist agents. The
application of insect-resist agents to wool apparel may be per-
ceived negatively by some consumers, despite the agents’ low
mammalian toxicity. Encapsulating these insecticides may give
extra reassurance to these consumers. The research carried out
in this area is quite negligible. Kettel et al. coated wool fabrics
with permethrin-embedded ␤-cylodextrin nanogel with controlled
release of permethrin [18]. Encapsulated citronella oil also has been
investigated as a mosquito repellent for cotton fabrics [19].
Encapsulation would allow the application of water-soluble
antimicrobial agents and insecticides with low to no affinity for
wool (i.e. they would not be absorbed into fibre), would reduce
their potential dermal toxicity, increase ease of handling, and also
would prolong their durability to washing. Moreover, conventional
antimicrobial and insect-resist treatments can produce an envi-
ronmental problem from the toxicity of aqueous effluent. This
is because the applied quaternary ammonium compounds only
50–95% are absorbed into wool depending on their chemical struc-
ture [15,16] and also insect-resist agents are not 100% absorbed
into the wool and the residual active in the effluent can be toxic to
some aquatic life [20]. Some effluent may need treatment before
discharging to main sewer or into a watercourse [21], but encap-
sulation has the potential to reduce contamination of this effluent.
Insecticides require low water solubility to be well absorbed by
wool in an aqueous dyebath by current methods. Some insecticides
with high water solubility, such as the neonicotinoid imidacloprid,
can be effective against wool-digesting insects [22]. This class of
insecticide could be practical if it could be applied to wool using an
application system not relying on aqueous dyebath uptake. Recent
investigations into alternative non-insecticidal insect-resist com-
pounds also indicate advantageous new approaches are possible
using encapsulation [23]. It is therefore clear that application of
insecticides in an encapsulated form may overcome many prob-
lems.
In this work, a neonicotinoid insecticide (clothianidin), and also
a synthetic pyrethroid (permethrin) in combination with a neon-
icotinoid (imidacloprid) were microencapsulated and applied to
wool fabrics to achieve durable insect-resist performance. Four
antibacterial agents including triclosan, dodecyltrimethylammo-
nium chloride (DTAC), PDPAC and chlorhexidine gluconate were
microencapsulated and applied to wool fabrics as they are proven
antibacterial agents with low toxicity. Several polymers including
chitosan, ethyl cellulose and polylactide have been investigated as
an encapsulating agent. The antimicrobial and antifungal activity
of the wool fabrics treated with these various microcapsules were
studied.
2. Experimental
2.1. Materials
The 100% wool fabric used was a 2/2 twill, having 34 ends/cm
and 24 picks/cm and weighed 210 g/m2 . Teric GN12 (non-ionic
detergent), and Sandozin MRN (wetting agent) were purchased
from Huntsman (USA) and Clariant Chemicals (Switzerland)
respectively. The selected insect-resist agents were clothiani-
din and imidacloprid supplied by Sumitomo Chemical (Japan)
and Meghmani Organics Limited (India) respectively, and per-
methrin supplied by Chemcolour Industries Limited (NZ). The
antibacterial agents used were triclosan or 5-chloro-2-(2,4-
dichlorophenoxy) phenol, dodecyltrimethylammonium chloride
(DTAC), poly(N,N-dimethyl-2-hydroxypropylammonium chloride)
or PDPAC (commercial name: Barquat PQ 2), and chlorhexidine
gluconate (CHG); the first two were supplied by Sigma-Aldrich
Chemicals Ltd. (USA) and the others were purchased from Lonza
Ltd. (Switzerland). Basolan MWP, a silicone resin, was purchased
from BASF Chemicals (Germany). Polylactide (PLA, Mn = 20,000,
melting temperature = 167 ◦ C and polydispersity = 1.1) was sup-
plied by Dow-Cargill (USA). Hercosett, an epoxy polyamide resin,
was supplied by Ashland Inc. (USA). Span 20 (sorbitan monolau-
rate), ethyl cellulose (viscosity = 170 mPa s of 5% solution in 80/20
mixture of toluene/ethanol at 25 ◦ C, ethoxyl content = 48.0–49.5%
(w/w) and glass transition temperature = 129–133 ◦ C) and chitosan
(85% deacetylated) were purchased from Sigma-Aldrich Chemical
Ltd. (USA).
Prior to treatments with encapsulated insect-resist and antimi-
crobial agents, the wool fabrics were scoured with 2 g/l Teric GN12
at 50 ◦ C for 20 min to remove processing oils and contaminants.
2.2. Encapsulation of antimicrobial and insect-resist agents
2.2.1. Encapsulation of DTAC
Chitosan was used to microencapsulate DTAC. A required quan-
tity of chitosan was dissolved in 20 ml of 1% acetic acid solution.
The required quantity of DTAC was added to it and was completely
dissolved. The ratio of DTAC to chitosan in the solution was 2:1 by
mass. The solution was then added to 100 ml of 1% dodecyl sulphate
solution drop-wise with vigorous stirring. Then 1 ml of glycerol
diglycidyl ether was added to crosslink the chitosan. After comple-
tion of the reaction, the capsules were recovered by centrifuging at
4000 rpm for two min.
2.2.2. Encapsulation of permethrin/imidacloprid
Ethyl cellulose was used to encapsulate the combination of
insecticides used in this work as both ethyl cellulose and the insec-
ticides are soluble in ethyl acetate, which made encapsulation easy.
The mass ratio of permethrin to imidacloprid in the capsules was
3:1. A required quantity of ethyl cellulose was dissolved in 15 ml
of ethyl acetate. The required quantity of permethrin and imida-
cloprid was added to it and was completely dissolved by stirring.
The ratio of permethrin/imidacloprid to ethyl cellulose was 2:1.
The solution was then added to 100 ml of 1% Span 20 solution
drop-wise. After completion of capsule formation, 1 ml of glycerol
diglycidyl ether was added to crosslink the ethyl cellulose. After
2 h, the reaction was completed and the capsules were separated
by centrifuging at 4000 rpm for 2 min.
2.2.3. Encapsulation of clothianidin, triclosan, PDPAC, and CHG
PLA was used as an encapsulating material to encapsulate cloth-
ianidin, triclosan, PDPAC, and CHG. A required quantity of PLA was
dissolved in 40 ml of dichloromethane to make a solution. In each
case the antibacterial or insect resist agent was added to the solu-
tion drop-wise and a solution was made by stirring. The ratio of
insecticidal and antimicrobial agents to PLA in the solution was
2:1 by mass. After formation, the microcapsules were separated
from solution by centrifuging at 4000 rpm for 2 min, and were re-
dispersed in water to apply them on wool fabric samples.
 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229
2.3. Application of encapsulated antimicrobials and insect-resist
agents to fabric
2.3.1. Clothianidin and permethrin–imidacloprid
The encapsulated permethrin/imidacloprid was dispersed in
170 ml of water containing 30 g/l Basolan MWP through stirring.
Four drops of Sandozin MRN were then added to the dispersion
microcapsules and a fabric sample was soaked in that dispersion
for 5 min. The fabric sample was then passed through a laboratory
pad mangle at 10 psi pressure at a speed of 2 m/min. The fabric was
then dried at 80 ◦ C for 4 min and cured at 120 ◦ C for 5 min. The con-
centration of encapsulated permethrin/imidacloprid was adjusted
so that the final concentration in the fabric would be 3.6 ppm on the
weight of wool (oww) permethrin and 1.2 ppm oww imidacloprid.
In the case of clothianidin, the application levels on wool fabrics
were 50, 100 and 200 ppm oww. The encapsulated clothianidin was
dispersed in 170 ml of water, and 20 g/l Hercosett resin was added
to it through stirring. Four drops of Sandozin MRN was then added
and a fabric sample was soaked in that dispersion for 5 min. The
fabric sample was then passed through a laboratory padding man-
gle at 10 psi pressure at a speed of 2 m/min. The fabric was dried at
80 ◦ C for 10 min.
2.3.2. Triclosan, DTAC, PDPAC, and CHG
The microcapsules of the antibacterial agents were dispersed
separately in water, and 30 g/l Basolan MWP was then added to the
dispersion of microcapsules through stirring. Four drops of San-
dozin MRN was then added and a fabric sample was soaked in that
dispersion for 5 min. The fabric sample was then passed through a
laboratory padding mangle at 10 psi pressure at a speed of 2 m/min.
The fabric was cured at 120 ◦ C for 5 min. The pick-up was adjusted
to 80% and the concentration of encapsulated antibacterial agents
in the padding solution was adjusted so that the level of antimi-
crobial agents on the treated fabric would be 0.5% oww. The fabric
samples were dried at 80 ◦ C for 5 min, and cured at 120 ◦ C for 3 min.
2.4. Assessment of antibacterial and insect-resist performance
The antibacterial properties of the treated and untreated wool
fabric samples were measured by the AATCC Test Method 147-1998
(Antibacterial Activity Assessment of Textile Materials: Parallel Streak
Method) against Staphylococcus aureus and Klebsiella pneumoniae
bacteria as they represent the most problematic Gram-positive and
Gram-negative pathogens. 1 ml of 24 h broth culture of bacteria
was mixed with 9 ml of sterile distilled water in a Petri dish and
one loopful of diluted inoculum was transferred to the surface of
the sterile agar plate by making 5 streaks, approximately 60 mm in
length and spaced 10 mm apart covering the central area of a stan-
dard Petri dish. Samples of fabric (25 mm × 50 mm) were gently
pressed transversely across the inoculum streaks to ensure inti-
mate contact with the agar plate and incubated at 37 ± 2 ◦ C for 24 h,
after which the interruption of bacterial growth along the streaks
of inoculum under the specimen and zone of inhibition beyond its
edge were examined. The bioassays of wool fabrics treated with
encapsulated permethrin/imidacloprid were conducted in accor-
dance with the Wools of New Zealand Test Method 25, which is
based on ISO 3998-1977. The exposure period for the bioassay was
14 days. In both test methods, at least three samples were tested
and the averages are reported here.
2.5. Durability of treatments to ageing and washing
The durability of the treatments to ageing was investigated by
storing the samples at 70 ◦ C in an oven for one week. The antibac-
terial or insect-resist performance of these fabrics was studied
without washing the samples. The durability of the treatment to
223
washing was studied up to 10 cycles of washing according to the
ISO 7A wash cycle at 40 ◦ C using a wool detergent named ‘Softly’
made by Pental Products Pty Ltd. (Australia). In the case of DTAC
microcapsules, the treated fabric was washed up to five times. After
being washed the fabrics were dried at 60 ◦ C for 15 min and their
antibacterial or insect-resist performance was studied.
2.6. Handle properties
The handle properties of the control and various microcapsules-
coated fabrics were assessed subjectively by a panel of six human
judges those had previous experience in assessing handle of vari-
ous textile substrates. The samples were ranked from the best to
the worst (ranked from 1 to 9) in terms of smoothness/softness.
The blank treated fabric without any microcapsules was used as a
control.
2.7. Optical and scanning electron microscopy (SEM)
To determine the size of the microcapsules, a Carl Zeiss Optical
Microscope, was used. One side of a thick plastic film was coated
with an adhesive and then dried microcapsules were sprayed on the
coated side. The microcapsule-coated surface was examined under
the light microscope. SEM was used to observe the morphology of
microcapsules made with chitosan and ethyl cellulose as encap-
sulating agents. A thick plastic film was coated with an adhesive
and then was coated with microcapsules. Microcapsules were bro-
ken down by rolling with a steel roller and the surface was then
sputter coated with gold to make it electro-conductive. It was then
examined by a SEM (Model JSM-6100, JEOL Corporation, Japan).
SEM was also used to observe the bonding of microcapsules to the
wool fibre surface. The fabric samples coated with microcapsules
by Hercosett resin before and after 5 cycles of International Wool
Secretariat (IWS) 7A washing were sputter-coated with gold and
examined on the same scanning electron microscope.
3. Results and discussion
3.1. Microcapsule formation and release of encapsulated
bioactive compounds
The produced capsules were in various sizes from microns to
nanometres in diameter depending on the encapsulating agents
used. However, all of the capsules produced were spherical in
shape. Fig. 1 shows optical micrographs of DTAC-loaded chitosan
and permethrin/imidacloprid-loaded ethyl cellulose microcap-
sules. It is evident that both types of capsule are smaller than 2 ␮m
in size. On the other hand, the size of the capsules of the PLA-
encapsulated permethrin were considerably larger compared to
the size of ethyl cellulose and chitosan encapsulated DTAC, PDPAC,
CHG and permethrin/imidacloprid. SEM was carried out to further
elucidate the exact size of the microcapsules produced by different
methods. Fig. 2 shows SEM micrographs of broken capsules. It can
be seen that generally the capsules are spherical in shape. In the
case of chitosan, the average size of the microcapsules is approx-
imately 0.8–2 ␮m and the thickness of the shell is approximately
0.15 ␮m. However, in the case of ethyl cellulose, the size of the cap-
sules is half of the size of chitosan capsules and the thickness of the
shell is 0.13 ␮m.
The release of antimicrobial and insect resist agents from chi-
tosan and ethyl cellulose capsules will take place either by pressure
or swelling induced by contact with water. Although the capsules
are crosslinked, still they will swell in contact with water and will
be disintegrated to release the actives. In the case of PLA as an
224 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229
Fig. 1. Optical micrographs of DTAC-loaded chitosan (top)
permethrin/imidacloprid-loaded ethyl cellulose (bottom) microcapsules.
encapsulating agent, the produced capsule will only release the
actives when they are ruptured by rubbing or by external pressure.
3.2. Insect-resistance performance
The insect-resistance of fabric treated with microencapsulated
permethrin/imidacloprid before and after washing is shown in
Table 1. It can be seen that in the case of the blank-treated control
fabric, only 5% of the larvae died. The control fabric was moder-
ately damaged and the mean mass loss of the sample fabric due to
feeding by T. bisselliella was 42.5 ± 4.3 mg. On the other hand, for
the permethrin/imidacloprid-treated wool all of the insects were
killed. No damage was visible with the treated fabric sample, and
the mean mass loss was only 0.8 ± 0.3 mg, or 1.9% of that of the
control. In the case of the treated fabric that had been washed, the
insect-resistance behaviour was similar to that of the unwashed
fabric, as the mean % mass loss only marginally increased to 2.4%
of that of the control. No pupation was observed for either the
control or the insect-resist microcapsule-treated fabrics. In sum-
mary, permethrin/imidacloprid microcapsule-treated wool fabric
showed an excellent insect resistance, and its insect-resistance was
not significantly diminished after washing. Results of the insect
bioassays on untreated fabric and fabrics treated with microen-
capsulated clothianidin at various levels before and after washing
are shown in Table 2. It can be seen that in the case of control
wool fabric, no larvae were killed. The control fabric was moder-
ately damaged and the mean mass loss of the sample fabric due
and
Fig. 2. SEM micrographs of DTAC-loaded chitosan (top), permethrin/imidacloprid-
loaded ethyl cellulose (middle), and permethrin-loaded PLA (bottom) microcap-
sules.
to feeding by T. bisselliella was 32.3 ± 0.5 mg. Although a control
mass loss of 35.0 mg is required for the bioassay to be declared
valid, the data still show a valid comparison between different
treatments. The 50 ppm clothianidin-treated wool fabric showed
a marked improvement over the control fabric, as 96.7% of the
insects were killed. We found that the minimum concentration
of permethrin and clothianidin required to achieve an acceptable
level of insect resistance was 50 ppm and concentrations lower
than that level reduces the mortality of insect to an unacceptable
level. No visible damage to the treated fabric sample was observed
and no measurable mass loss was observed. After 10 wash cycles
using IWS 7A washing protocol, the insect-resistance performance
of the 50 ppm clothianidin-treated fabric slightly diminished as
the mean mortality of larvae decreased to 85% and the mean %
mass loss was increased to 14% of that of the control. After 7
days of ageing the 50 ppm clothianidin-treated wool fabric also
showed an excellent insect-resist performance, with a mean mor-
tality of 88.3%, and no measurable mass loss. At 100 and 200 ppm
application levels, before washing the mortality was shown to be
100% but after washing, mortality considerably decreased to 56.7
and 60% for the 100 and 200 ppm respectively. The corresponding
 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229 225

Table 1
Bioassay of Tineola bisselliella on untreated and permethrin/imidacloprid microcapsule-treated wool fabrics before and after 10 washing.

Sample Mean % mortality Mean mass loss (mg) Mean % mass lossa Visual assessment Pass (P), fail (F) or borderline (B)

Control 5.0 42.5 ± 4.3 n.a. Moderate damage F

Treated 100.0 0.8 ± 0.3 1.9 No detectable damage P
Treated + hand-washed 100.0 1.0 ± 0.7 2.4 No detectable damage P
*** ***
F-Test (p < 0.05) – – –
LSD (0.05) 4.9 9.2 – – –
a
As a percentage of the mean voracity control, n.a., not applicable; LSD, least significant difference; n.s., not significant.
***
Significant at p ≤ 0.001.

Table 2
Bioassay of Tineola bisselliella on untreated and micro-encapsulated clothianidin-treated wool fabrics before and after 10 washes.

Sample Mean % mortality Mean mass loss (mg) Mean % mass Visual assessment Pass (P) or fail
lossa (F)

Control 0.0 32.3 ± 0.5 n.a. Very heavy damage with holes F
50 ppm clothianidin (unwashed) 96.7 −1.0 ± 0.5 −3.2 No detectable damage P
50 ppm clothianidin (unwashed but aged) 88.3 −1.4 ± 0.5 −4.3 No detectable damage P
50 ppm clothianidin (washed) 85.0 4.6 ± 1.6 14.4 Very slight visible cropping P
100 ppm clothianidin (unwashed) 96.7 −1.7 ± 0.1 −5.1 No detectable damage P
100 ppm clothianidin (unwashed but aged) 100.0 −1.5 ± 0.7 −4.6 No detectable damage P
100 ppm clothianidin (washed) 56.7 13.2 ± 0.2 40.8 Moderate cropping. Yarns and F
fibres severed
200 ppm clothianidin (unwashed) 93.3 −2.0 ± 0.3 −6.1 No detectable damage P
200 ppm clothianidin (unwashed but aged) 96.7 −1.5 ± 0.2 −4.8 No detectable damage P
200 ppm clothianidin (washed) 60.0 11.6 ± 4.4 36.0 Moderate cropping. F
Yarns/fibres partially severed
F-test (p ≥ 0.05) *** ***

LSD (0.05) 13.3 4.9

a
LSD, least significant difference; n.a., not applicable. As a percentage of the mean voracity control.
***
Significant at p ≤ 0.001.

mean mass loss of wool also increased from −4.6 and −4.8% to
40.8 and 36.0% respectively. The best insect-resist performance
after washing was shown by clothianidin at 50 ppm level and the
developed treatment was durable to at least 10 washes. Applied
dosage of clothianidin over 50 ppm oww showed lower durability
to washing perhaps due to the presence of some clothianidin on
the outer surface of the microcapsules that was removed during
washing.
3.3. Antibacterial performance
The antibacterial properties of the wool fabric treated with
encapsulated DTAC before and after five washes are shown in
Table 3. It can be seen that compared to the control, the treated
fabrics showed excellent antibacterial performance. In the case of
control fabric, there was bacterial growth directly under the fab-
ric sample, and also up to the edge of the fabric for both S. aureus
and K. pneumoniae and no inhibition zone was visible. This was
not unexpected as untreated wool fabric does not have antibacte-
rial properties. In the case of unwashed encapsulated DTAC-treated
fabrics, no bacterial growth was visible near the edge or directly
under the fabric samples for both bacteria investigated and the
observed zone of bacterial inhibition was 3 and 2 mm for S. aureus
and K. pneumoniae respectively. On the other hand, for the washed
sample, similar behaviour was observed but the zone of inhibition
was 2 mm for both types of bacteria. No significant difference in
antibacterial performance before and after washing was observed.
Therefore, it can be concluded that the DTAC microcapsule-treated
samples showed strong antibacterial performance that was resis-
tant to washing. We found that the concentration of DTAC in the
fabric should be at least 0.5% oww, as below this growth of bac-
teria was observed directly under the sample. The antibacterial
properties of wool fabric samples treated with encapsulated tri-
closan, CHG and poly (N,N-dimethyl-2-hydroxypropylammonium
chloride) before and after 10 washes, and also after 7 days age-
ing at 70 ◦ C are shown in Tables 4–6. It can be seen that compared
to the control, the treated fabrics showed excellent antibacterial
performance.
Triclosan showed excellent antibacterial efficacy before and
after 10 cycles of washing and also after 7 days of ageing. The size of

Table 3
Antibacterial performance of wool fabric treated with encapsulated DTAC before and after 5 washes.

Treatments Staphylococcus aureus Klebsiella pneumoniae

Bacterial Width of inhibition Bacterial Width of inhibition

growth zone (mm) growth zone (mm)

Control, untreated Visible growth directly 0 Visible growth directly 0

fabric under the fabric under the fabric
DTAC-treated fabric No growth near the 3.0 No growth near the 2.0
before washing edge or under the edge or under the
fabric fabric
DTAC-treated fabric No growth near the 2.0 No growth near the 2.0
after washing edge or under the edge or under the
fabric fabric
226 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229

Table 4
Antibacterial performance of wool fabric treated with encapsulated triclosan after 7 days of ageing and 10 washes.

Treatments Staphylococcus aureus Klebsiella pneumoniae

Bacterial growth Width of inhibition Bacterial growth Width of inhibition

zone (mm) zone (mm)

Control Visible growth directly 0 Visible growth directly 0

under the fabric under the fabric
Treated sample before washing No growth near the 8.0 No growth near the 5.0
edge or under the edge or under the
fabric fabric
Treated sample after washing No growth near the 2.0 No growth near the 2.0
edge or under the edge or under the
fabric fabric
Treated sample after ageing No growth near the 10.0 No growth near the 5.0
edge or under the edge or under the
fabric fabric

Table 5
Antibacterial performance of wool fabric treated with encapsulated PDPAC after 7 days of ageing and 10 washes.

Treatments Staphylococcus aureus Klebsiella pneumoniae

Bacterial growth Width of inhibition Bacterial growth Width of inhibition

zone (mm) zone (mm)

Control Visible growth directly 0 Visible growth directly 0

under the fabric under the fabric
Treated sample before washing No growth near the 10.0 No bacterial growth 1.0
edge or under the near the edge or under
fabric the fabric
Treated sample after washing No growth near the 5.0 No growth near the 2.0
edge or under the edge or under the
fabric fabric
Treated sample after ageing No growth near the 5.0 No growth near the 2.0
edge or under the edge or under the
fabric fabric

inhibition zone slightly decreased, which may indicate a decrease
in antibacterial performance, but as the size of the inhibition zone
is still large, the antibacterial performance shown is adequate. It
can be seen that in the case of 7-day ageing, the size of the inhibi-
tion zone slightly increased, indicating that due to the long thermal
treatment some triclosan molecules may have bloomed to the sur-
face of the microcapsules. The best antibacterial performance was
shown by the PDPAC, especially after washing, as the size of the
inhibition zone in the cases of S. aureus and K. pneumoniae was
5.0 and 2.0 mm respectively. The poorest performance was shown
by CHG, which showed very poor antibacterial activity against K.
pneumoniae as slight growth of bacteria under the test sample was
observed. Overall, the best antibacterial performance was shown
by PDPAC.
Literatures published in the area of application of encapsulated
synthetic antimicrobial agents are few. Goetzendorf-Grabowska
et al. applied PLA-encapsulated triclosan to nonwoven viscose
fabric at 1.3% on the weight of fabric [24]. They found that
the zone of inhibition extended to 18–21 and 6–14 mm for S.
aureus and E. coli respectively, but did not mention durability to
laundering. Previous investigation on application of three quater-
nary ammonium compounds including cetylpyridinium chloride,
cetyltrimethylammonium bromide and benzyldimethylhexadecy-
lammonium chloride by ionic bonding showed that the treated
fabric lost antimicrobial activity after 10 washings [16]. Here in this
work, we showed that by encapsulation, the release of antimicro-
bial agents can be delayed as the treated fabrics showed acceptable
levels of antimicrobial activity after 10 washings.

Table 6
Antibacterial performance of wool fabric treated with encapsulated CHG after 7 days of ageing and 10 washes.

Treatments Staphylococcus aureus Klebsiella pneumoniae

Bacterial growth Width of inhibition Bacterial growth Width of inhibition

zone (mm) zone (mm)

Control Visible growth directly 0 Visible growth directly 0

under the fabric under the fabric
Before washing No growth near the 3.0 No growth near the 1.0
edge or under the edge or under the
fabric fabric
After washing No growth near the 3.0 Some growth near the 0
edge or under the edge or under the
fabric fabric
After ageing No growth near the 4.0 No growth near the 3.0
edge or under the edge or under the
fabric fabric
 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229 227

Fig. 3. SEM micrographs of wool fabrics treated with DTAC (1% oww)-loaded chitosan (top) and permethrin/imidacloprid (100 ppm oww clothianidin)-loaded ethyl cellulose
(bottom) microcapsules before and after 10 cycles of washing.

Fig. 4. SEM images of wool fabrics treated with microcapsules loaded with insect-resist and antibacterial agents before and after 10 cycles of washing. Prefix: B = 1% PDPAC
capsule; G = 1% oww CHG; T = 1% triclosan. Suffix: T = before washing; W = after washing.
228 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229

Table 7
Rankings of softness/smoothness (1–9: best to worst) of unwashed fabric samples.

Sample ID Rankings by six human judges

1 2 3 4 5 6 Mean

Control fabric treated with Basolan MW only 1 2 2 1 2 1 1.5

DTAC capsules with Basolan MWP (before washed) 6 3 4 3 6 4 4.3
DTAC capsules with Basolan MWP (after washed) 2 1 5 4 1 3 2.7
CHG capsules with Basolan MWP (before washed) 5 7 7 6 7 5 6.2
CHG capsules with Basolan MWP (after washed) 3 4 3 5 3 2 3.3
PDPAC capsules with Basolan MWP (before washed) 7 6 1 7 5 6 5.3
PDPAC capsules with Basolan MWP (after washed) 4 5 6 2 4 7 4.7
Clothianidin capsules with Basolan MWP (before washed) 9 9 9 8 9 8 8.7
PDPAC capsules with Basolan MWP (after washed) 8 8 8 9 8 9 8.3

3.4. Handle properties 4. Conclusions

All the antibacterial treated fabrics showed fairly similar han-
dle properties (softness) as all treatments were bonded to wool
using the same Basolan MWP polymer but showed slightly poor
handle compared to the Basolan-treated control fabric (Table 7).
The handle properties improved slightly after washing. The han-
dle properties of the clothianidin microcapsule-treated wool
fabric showed poor handle properties as it was treated with
Hercosett resin which is known to affect handle properties of
wool fabric. The handle properties did change even after wash-
ing.
3.5. Surface morphology of microcapsules and various
antimicrobial and insect-resist agents-loaded
microcapsule-treated wool fabrics
Novel polymeric encapsulation procedures have been devel-
oped to encapsulate various antibacterial and insect-resist agents,
including highly water soluble agents, to prolong their perfor-
mance on wool. Microencapsulated PDPAC showed the best overall
antibacterial performance after 10 cycles of ISO 7A washing and
also after ageing. The encapsulated clothianidin showed the best
insect-resist performance at a level of 50 ppm oww and passed
the Wools of New Zealand Test Method 25, even after 10 cycles
of washing. The washed fabric showed 85% mortality and the mean
mass loss was only 4.6 mg. The encapsulated permethrin and imi-
dacloprid performed equally well. The handle properties were only
slightly affected by the treatments.
Acknowledgements

Fig. 2 shows optical micrographs of chitosan and ethyl cellu-
lose microcapsules loaded with DTAC and permethrin/imidacloprid
respectively. It is evident that the microcapsules are sphere-shaped
and only few microns to nm in size. For more precise measure-
ment of shape and size of the various microcapsules, SEM was
carried out after applying them on wool fabric. SEM images of
wool fabrics treated with DTAC-loaded chitosan microcapsules
before and after 10 cycles of IWS 7A washing is shown in Fig. 3.
It is evident that microcapsules were firmly bound to wool fibre
surface by silicone resin (Basolan MW-P). However after 10 wash-
ings, some silicone resins were removed and the microcapsules
were exposed. This could be the reason that after washing the
DTAC-loaded microcapsule-treated wool fabric showed higher
inhibition zone compared to the inhibition zone showed by the
same fabric before washing. It is also evident that the micro-
capsules were less than micrometre in size. Fig. 4 shows SEM
micrographs of wool fabric samples treated with various insect-
resist and antibacterial agents-loaded microcapsules before and
after washing. It can be seen that the clothianidin-loaded PLA
microcapsules were approximately 2 ␮m in size, which is desir-
able as they are smaller than the mouth of the insect larvae, and
are therefore difficult to avoid ingesting along with the wool. On
the other hand, PDPAC, triclosan and CHG-loaded PLA microcap-
sules were approximately 0.5–2 ␮m in size. It can also be seen
that the capsules were evenly dispersed on the wool fibre sur-
face. The capsules were retained on the fabric after 10 washing
cycles as shown in Figs. 3–4. As the microcapsules were mixed
with Basolan MWP, they were not clearly visible as they were cov-
ered by the polymer. Basolan MWP formed a smooth layer over
the capsule layer. It is evident that even after 10 washing cycles,
no removal of Basolan MWP was observed as surfaces looked quite
similar before and after washing. The antibacterial results and SEM
images showed that the binding treatment of microcapsules to
the wool fibre surface was durable to at least 10 cycles of IWS 7A
washes.
The authors wish to acknowledge the funding received from
Australian Wool Innovation Limited and also from the Ministry of
Business, Innovation and Employment (MBIE) of the New Zealand
Government thorough contract C10X0824. We would like to thank
Stewart Collie of AgResearch Limited for editing this manuscript.
References
[1] S Gupta (Ed.), Smart Textiles – Their Production and Marketing Strategies,
National Institute of Fashion Technology, Delhi, India, 2000.
[2] D. Gupta, Design and engineering of functional clothing, Indian J. Fibre Text.
Res. 36 (2011) 327–335.
[3] N. Pan, G. Sun, Functional Textiles for Improved Performance, Woodhead Pub-
lishing, Cambridge, 2011.
[4] J. Zhang, B. Li, L. Wu, A. Wang, Facile preparation of durable and robust superhy-
drophobic textiles by dip coating in nanocomposite solution of organosilanes,
Chem. Commun. 49 (2013) 11509–11511.
[5] J.D. Pyne, D.W. Kudner, A durable antiodour finish for cotton textiles, Text.
Chem. Color. 28 (1996) 28–30.
[6] E. Irzmanska, G. Padula, R. Irzmanski, Impedance plethysmography as a tool
for assessing exertion-related blood flow changes in the lower limbs in healthy
subjects, Measurement 47 (2014) 110–115.
[7] B.L. Zenitz, Quaternary ammonium salts as antimicrobial agents, Science 112
(1950) 2911–2913.
[8] A.J. Isquith, A. Abbot, P.A. Walters, Surface-bonded antimicrobial activity of an
organo-silicone quaternary ammonium chloride, Appl. Microbiol. 24 (1972)
859–863.
[9] M. Orhan, D. Kut, C. Gunesoglu, Use of triclosan as antibacterial agent in textiles,
Indian J. Fibre Text. Res. 32 (2007) 114–118.
[10] Y. Qin, Silver streak, Text. Horizons November–December (2005) 16–17.
[11] C.L. Fox, S.M. Modak, Mechanism of silver sulfadiazine on burn wound infec-
tions, Antimicrob. Agents Chemother. 5 (1974) 582–588.
[12] T.M. Benn, P. Westerhoff, Nanoparticles silver released into water from com-
mercially available sock fabrics, Environ. Sci. Technol. 42 (2008) 4133–4139.
[13] L. Geranio, M. Heuberger, B. Nowack, The behaviour of silver nanotextiles dur-
ing washing, Environ. Sci. Technol. 43 (2009) 8113–8118.
[14] P. Saraswathi, P.N. Krishnan, C. Dilip, Antimicrobial activity of cotton and silk
fabric with herbal extract by micro encapsulation, Asia-Pac. J. Trop. Med. 3
(2010) 128–132.
[15] T. Zhao, G. Sun, Antimicrobial finishing of wool fabrics with quaternary amino-
pyridinium salts, J. Appl. Polym. Sci. 103 (2007) 482–486.
[16] P. Zhu, G. Sun, Antimicrobial finishing of wool fabrics using quaternary ammo-
nium salts, J. Appl. Polym. Sci. 93 (2004) 1037–1041.
 M.M. Hassan, M. Sunderland / Progress in Organic Coatings 85 (2015) 221–229
[17] F. Özyildiz, S. Karagönlü, G. Basal, A. Uzel, O. Bayraktar, Micro-encapsulation
of ozonated red pepper seed oil with antimicrobial activity and application to
nonwoven fabric, Lett. Appl. Microbiol. 56 (2013) 168–179.
[18] M.J. Kettel, K. Schaefer, J. Groll, M. Moeller, Nanogels with high active
␤-cyclodextrin content as physical coating system with sustained release prop-
erties, ACS Appl. Mater. Interfaces 6 (2014) 2300–2311.
[19] M.M. Miró Specos, G. Escober, P. Marino, Aroma finishing of cotton fabrics by
means of microencapsulation techniques, J. Indian Text. 40 (2010) 13–32.
[20] D. Allanach, T. Shaw, Moth proofing and the environment, in: Proceedings
of TIFCON 1989 – Carpets What’s afoot? Conference of the Textile Institute’s
Floorcoverings Group, Blackpool, United Kingdom, 1989.
229
[21] P.E. Ingham, S.J. McNeil, M.R. Sunderland, Functional finishes for wool – eco
considerations, Adv. Mater. Res. 441 (2012) 33–43.
[22] J. Haas, Development of novel insect-resist-agent for keratin digesting insects
Proceedings of the 8th International Wool Textile Research Conference, vol. 4,
Christchurch, New Zealand, 1990, pp. 558–567.
[23] M.R. Sunderland, R.H. Cruickshank, S.J. Leighs, The efficacy of antifungal azole
and antiprotozoal compounds in protection of wool from keratin-digesting
insect larvae, Text. Res. J. 84 (2014) 924–931.
[24] B. Goetzendorf-Grabowska, H. Królikowska, P. Bak, ˛ M. Gadzinowski, B. Brycki, A.
Szwajca, Triclosan encapsulated in poly(l,l-lactide) as a carrier of antibacterial
properties of textiles, Fibres Text. East. Eur. 16 (2008) 102–107.