Textile Research Journal
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Recent Advances in Antimicrobial Treatments of Textiles
Yuan Gao and Robin Cranston
Textile Research Journal 2008; 78; 60
DOI: 10.1177/0040517507082332
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Textile Research Journal
Article
Recent Advances in Antimicrobial Treatments of Textiles
Yuan Gao1 and Robin Cranston
Abstract
The growth of microbes on textiles
during use and storage negatively affects the
wearer as well as the textile itself. The detrimental
effects can be controlled by durable antimicrobial
finishing of the textile using broad-spectrum biocides or by incorporating the biocide into synthetic fibers during extrusion. Consumers’ attitude
towards hygiene and active lifestyle has created a
rapidly increasing market for antimicrobial textiles,
which in turn has stimulated intensive research
and development. This article reviews the requirements for antimicrobial finishing, qualitative and
quantitative evaluations of antimicrobial efficacy,
the application methods of antimicrobial agents
and some of the most recent developments in antimicrobial treatments of textiles using various active
agents such as silver, quaternary ammonium salts,
polyhexamethylene biguanide, triclosan, chitosan,
dyes and regenerable N-halamine compounds and
peroxyacids. Examples of commercial antimicrobial products are presented to illustrate the active
agents used and their finishing methods.
Division of Textile and Fibre Technology,
Commonwealth Scientific and Industrial Research
Organization (CSIRO), Bayview Ave, Clayton 3168,
Australia
Key words
textile, fiber, fabric, antimicrobial,
antibacterial, biocide
Textiles have long been recognized as media to support the
growth of microorganisms such as bacteria and fungi. These
microorganisms are found almost everywhere in the environment and can multiply quickly when basic requirements,
such as moisture, nutrients and temperature are met. Most
synthetic fibers, due to their high hydrophobicity, are more
resistant to attacks by microorganisms than natural fibers
[1]. Proteins in keratinous fibers and carbohydrates in
cotton can act as nutrients and energy sources under certain conditions. Soil, dust, solutes from sweat and some
textile finishes can also be nutrient sources for microorganisms [1].
The growth of microorganisms on textiles inflicts a
range of unwanted effects not only on the textile itself but
also on the wearer. These effects include the generation of
unpleasant odor, stains and discoloration in the fabric, a
reduction in fabric mechanical strength and an increased
Textile Research Journal Vol 78(1): 60–72 DOI: 10.1177/0040517507082332
likelihood of contamination [1]. For these reasons, it is
highly desirable that the growth of microbes on textiles be
minimized during their use and storage.1
Consumers’ demand for hygienic clothing and activewear
has created a substantial market for antimicrobial textile
products. Estimations have shown that the production of
antimicrobial textiles was in the magnitude of 30,000 tones
in Western Europe and 100,000 tones worldwide in 2000
[2, 3]. Furthermore, it was estimated that the production
increased by more than 15% a year in Western Europe
between 2001 and 2005, making it one of the fastest growing sectors of the textile market [4]. Sportswear, socks,
shoe linings and lingerie accounted for 85% of the total
1
Corresponding author: tel: +61-3-9545 2104; fax: +61-3-9545
2363; e-mail: yuan.gao@csiro.au
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Los Angeles, London, New Delhi and Singapore
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Recent Advances in Antimicrobial Treatments of Textiles Y. Gao and R. Cranston
production [2, 3]. There is also a broader market for antimicrobial fibers, for instance, in outdoor textiles, air filters,
automotive textiles, domestic home furnishings and medical textiles. This high demand, in turn, has stimulated
intensive research and development. Some earlier work in
antimicrobial textiles has been briefly reviewed by Purwar
and Joshi [1] and Williams et al. [5]. Since then a large
number of papers and patents have been published. In this
article, we summarize some of the most recent development in antimicrobial treatments of synthetic, cotton and
wool fabrics or fibers using various active agents, and the
methods for the evaluation of antimicrobial efficacy. Numerous antimicrobial textile products have been launched on
the market by leading manufacturers. Examples are presented to illustrate the active agents used in these products
and their application methods.
Requirements for Antimicrobial
Finishing
In order to obtain the greatest benefit, an ideal antimicrobial treatment of textiles should satisfy a number of requirements [1, 5]. Firstly, it should be effective against a broad
spectrum of bacterial and fungal species, but at the same
time exhibit low toxicity to consumers, e.g. not cause toxicity, allergy or irritation to the user. Antimicrobial-treated
textiles have to meet standards in compatibility tests (cytotoxicity, irritation and sensitization) before marketing. Secondly, the finishing should be durable to laundering, dry
cleaning and hot pressing. This is the greatest challenge as
textile products are subjected to repeated washing during
their life. Thirdly, the finishing should not negatively affect
the quality (e.g. physical strength and handle) or appearance of the textile. Finally, the finishing should preferably
be compatible with textile chemical processes such as dyeing, be cost effective and not produce harmful substances to
the manufacturer and the environment.
One further consideration is that the antimicrobial finishing of textiles should not kill the resident flora of nonpathogenic bacteria on the skin of the wearer. The skin
resident flora consists of several bacterial genera, which
are important to the health of the skin as they lower skin
surface pH and produce antibiotics to create an unfavorable environment for the growth of pathogenic bacteria [6].
Fortunately, antimicrobial agents on textiles may only
reduce the density of the skin resident flora but do not
completely eliminate them. To date, no evidence exists that
the use of antimicrobial textiles changes the ecology of
skin resident flora leading to the outgrowth of pathogenic
bacteria [6].
61
Modes of Antimicrobial Action
A living microbe (e.g. bacterium, fungus) typically has an
outermost cell wall which is mainly composed of polysaccharides. This cell wall maintains the integrity of cellular
components and shields the cell from the extracellular
environment. Immediately beneath the cell wall is a semipermeable membrane which encloses intracellular organelles
and a myriad of enzymes and nucleic acids. The enzymes
are responsible for the chemical reactions that take place
within the cell, and the nucleic acids store all of the genetic
information of the organism. The survival or growth of
microorganisms depends on the integrity of the cell and
the concerted action and proper state of all of these components. Antimicrobial agents either inhibit the growth
(-static) or kill (-cidal) the microorganisms. Almost all antimicrobial agents used in commercial textiles, e.g. silver,
triclosan, polyhexamethylene biguanide (PHMB) and
quaternary ammonium compounds, are biocides. They damage the cell wall or alter cell membrane permeability, denature proteins, inhibit enzyme activity or inhibit lipid synthesis,
all of which are essential for cell survival. The mechanisms
of biocides used on commercial textiles are discussed in the
following sections.
Application of Antimicrobial Agents
Various methods, depending on the particular active agent
and fiber type, have been developed or are under development to confer antimicrobial activity to textiles. For synthetic
fibers, the antimicrobial active agents can be incorporated
into the polymer prior to extrusion or blended into the fibers during their formation. Such processing provides the
best durability as the active agent is physically embedded in
the structure of the fiber and released slowly during use.
This method of fabrication has been adopted by some manufacturers, such as the silver-containing Bioactive® polyester fibers developed by Trevira and the triclosan-containing
Silfresh® cellulose acetate fibers manufactured by Novaceta. The conventional exhaust and pad–dry–cure processes
have been used for antimicrobial finishing on natural as
well as synthetic fibers for the biocides such as triclosan [7]
and PHMB [8, 9]. Padding, spraying and foam finishing
have been used for the silicone-based quaternary agent
AEM 5700 [10]. Many other methods have been reported,
such as the use of nanosized colloidal solutions [11], nanoscale shell–core particles [12, 13], chemical modification of
the biocide for covalent bond formation with the fiber [14,
15], crosslinking of the active agent onto the fiber using a
crosslinker [16, 17] and polymerization grafting [18]. These
methods are further illustrated in the following sections.
An emerging method for antimicrobial finishing is to use
the sol-gel process which allows the fabrication of materi-
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als with a large variety of properties: ultra-fine powders,
monolithic ceramics and glasses, ceramic fibers, inorganic
membranes, thin film coatings and aerogels. Sol-gel has
been extensively explored for applications such as coating
[19]. It is claimed that sol-gel technology can enable the
coating of textiles with almost unlimited functionality by
incorporating functional agents into the sol-gel nanoparticles [20, 21]. With regards to antimicrobial ability, several
biocides have been encapsulated in sol-gel particles which
are then coated onto textile products to provide the
desired functionality [20, 22].
Evaluation of Antimicrobial Efficacy
A number of test methods have been developed to determine the efficacy of antimicrobial textiles [23, 24, 25]. These
methods generally fall into two categories: the agar diffusion test and suspension test. The bacterial species Staphylococcus aureus (Gram positive) and Klebsiella pneumoniae
(Gram negative) are recommended in most test methods.
These two species are potentially pathogenic and therefore
require proper physical containment facilities for handling
(e.g. a biosafety cabinet). Many studies have used the innocuous Escherichia coli (Gram negative) as a test microorganism which can be cultured and handled in a standard
laboratory with minimal health risk.
Agar Diffusion Test
The agar diffusion tests include AATCC 147-2004 (American Association of Textile Chemists and Colorists), JIS L
1902-2002 (Japanese Industrial Standards) and SN 1959201992 (Swiss Norm). They are only qualitative, but are simple to perform and are most suitable when a large number
of samples are to be screened for the presence of antimicrobial activity. In these tests, bacterial cells are inoculated on
nutrient agar plates over which textile samples are laid for
intimate contact. The plates are then incubated at 37°C for
18–24 h and examined for growth of bacteria directly underneath the fabrics and immediately around the edges of the
fabrics (zone of inhibition). No bacterial growth directly
underneath the fabric sample indicates the presence of
antimicrobial activity. The zone of inhibition should not be
expected if the antimicrobial agent is firmly attached to the
textile (e.g. covalently) which prevents its diffusion into the
agar. If the antimicrobial agent can diffuse into the agar, a
zone of inhibition becomes apparent and its size provides
some indication of the potency of the antimicrobial activity
or the release rate of the active agent.
Suspension Test
This type of test is exemplified by AATCC 100-2004, JIS L
1902-2002 and SN 195924-1992. These methods provide
quantitative values on the antimicrobial finishing, but are
more time-consuming than agar diffusion tests. Typically, a
small volume (e.g. 1 ml) of bacterial inoculum in a growth
media is fully absorbed into fabric samples of appropriate
size without leaving any free liquid. This ensures intimate
contact between the fabric and the bacteria. After incubating the inoculated fabrics in sealed jars at 37°C or 27°C for
up to 24 h, the bacteria in the fabric are eluted and the
total number is determined by serial dilution and plating
on nutrient agar plates. Antimicrobial activity, expressed as
percentage of reduction, is calculated by comparing the
size of the initial population with that following the incubation. Appropriate controls, e.g. samples that have gone
through the same processing except the antimicrobial finishing, should be included in each experiment to ascertain
that the observed decrease in bacterial number is truly due
to the antimicrobial finishing. Choosing a calculation equation may be important. It has been observed that two different equations can produce very different results for the
same set of data [9].
It should be noted that suspension tests are often performed under artificial conditions that promote bacterial
growth (e.g. rich nutrients in the inoculum and saturating
moisture in the testing fabrics). The moisture in the tests is
also essential for the action of the biocide. As a result, dramatic results are often produced (e.g. >99% bacterial cells
are killed during the assays), leading to an overwhelming
impression of the efficacy of the antimicrobial ability. However, such conditions are rarely found during the normal
use of a textile product. To date, very few studies have examined the antimicrobial effects under normal wearing conditions. To more closely mimic the real-life situation, the JIS
L 1902-2002 method recommends the use of bacterial cells
suspended in heavily diluted nutrient media to limit nutrient levels. The ISO (International Organization for Standardization) has developed a test method (ISO 20743) in
which bacteria are “printed” onto the surface of textiles
without them being in an aqueous suspension [25, 26]. The
printed samples are then incubated under humid conditions at 20°C for a specified time (18–24 h) following which
the surviving cells are counted.
Antimicrobial tests only assess the antimicrobial effectiveness of the treated textiles. Before marketing, the textile products have to pass biocompatibility tests which
involve three separate assays: cytotoxicity, sensitization
and irritation. These assays are outside the scope of this
review but are discussed elsewhere [23, 24].
Antimicrobial Agents for Textiles
Several major classes of antimicrobial agents are used in
the textile industry. They are generally not new per se and
have been in use in other industries, e.g. as food preserva-
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Recent Advances in Antimicrobial Treatments of Textiles Y. Gao and R. Cranston
tives, disinfectants, swimming pool sanitizers or in wound
dressings. These agents are potent in their bactericidal
activity, as indicated by their Minimal Inhibitory Concentration (MIC) values. However, their attachment to a textile surface or incorporation within the fiber substantially
reduces their activity and limits their availability. Furthermore, the biocide can be gradually lost during the use and
washing of the textile. For these reasons, large amounts of
these biocides need to be applied to textiles to effectively
control bacterial growth and to sustain durability.
Metals and Metal Salts
Many heavy metals are toxic to microbes at very low concentrations either in the free state or in compounds. They
kill microbes by binding to intracellular proteins and inactivating them [27]. Although some other metals, such as
copper [28], zinc [29, 30] and cobalt [31], have attracted
attention as effective antimicrobial agents for textiles, silver is by far the most widely used in general textiles [1, 5] as
well as in wound dressings [32]. It has a MIC value of 0.05–
0.1 mg/l against E. coli [33]. Some concerns have been
expressed about the development of bacterial resistance to
silver [34, 35].
For synthetic fibers, silver particles can be incorporated
into the polymer before extrusion [36] or before nanofiber
formation using electrospinning [37, 38]. During use, silver
diffuses onto the surface of the fiber and forms silver ions
in the presence of moisture. The rate of silver release can
be influenced by the chemistry and physical characteristics
of the fiber and the amount of silver in the fiber. Gradual
release can lead to an extended period of biocidal activity
[5]. Apart from direct incorporation, nanosized silver in
colloidal solution has been padded onto synthetic and cellulosic fabrics to achieve a durable finishing [11]. Silver has
also been directly absorbed into pre-formed SeaCell®
Active, a fiber made of cellulose from certain seaweeds
with a large capacity for absorbing minerals [39].
The treatment of natural fibers with metals can only be
undertaken at the finishing stage and various strategies
have been devised to enhance the uptake and durability.
Cotton has been pretreated with succinic acid anhydride,
which acted as ligand for metal ions to enhance the subsequent adsorption of metallic salts (Ag+ and Cu2+) and to
provide very effective antibacterial activity [40]. In protein fibers (e.g. wool), the free carboxyl groups of aspartyl
and glutamyl residues are considered the most likely
binding sites for metal ions. The binding capacity can be
further enhanced by pre-treatment with tannic acid which
increases the number of binding sites, or with EDTA dianhydride which has chelating ability towards metal ions [41,
42, 43]. However, such treatments of textiles with metal
ions have serious limits due to technical and environmental
problems and therefore have not been adopted in commercial production.
63
Recent breakthroughs in technology have overcome
cost, environmental and technical challenges associated
with producing some metal treated textiles on a commercial scale. As a result, silver is now used in a large number of
commercial antimicrobial synthetic fibers and yarns. For
example, Thomson Research Associates manufactures UltraFresh® and Silpure® products. The silver is in the form of
ultra-fine metallic particles and is primarily applied to polyester fabrics at the finishing stage. Milliken has developed
a silver-based antimicrobial agent, AlphaSan®, which is a zirconium phosphate-based ceramic ion-exchange resin containing silver and is added during the extrusion process of
synthetic fibers. AlphaSan® is being used by a number of
companies to produce antimicrobial textiles, for examples,
the polyester and nylon yarn by O’Mara (MicroFresh® and
SoleFresh®) and the polyester yarn by Sinterama (GuardYarn®). AgION Technologies produces silver-based antimicrobial textiles using an ion-exchange mechanism. In this
procedure, silver ions are manufactured into multi-faceted
zeolite carriers which are then incorporated into a polymer
or coating. Under conditions that support bacterial growth,
silver ions in the zeolite are exchanged with sodium ions
present in ambient moisture to control bacterial growth
[44]. In addition, The Bioactive® polyester fibers produced
by Trevira also have silver incorporated into the fibers. Very
recently, silver finishing was extended to wool on a commercial scale by Nanohorizon Inc. [45]. In this treatment,
silver nanoparticles (SmartSilver®) are applied to wool
using typical fabric and garment dye systems. The original
properties of the wool, including handle and dyeability,
remain unchanged after the treatment.
Quaternary ammonium compounds
Quaternary ammonium compounds (QACs), particularly
those containing chains of 12–18 carbon atoms, have been
widely used as disinfectants [27]. These compounds carry a
positive charge at the N atom in solution and inflict a variety of detrimental effects on microbes, including damage
to cell membranes, denaturation of proteins and disruption
of the cell structure [27]. During inactivation of bacterial
cells, the quaternary ammonium group remains intact and
retains its antimicrobial ability as long as the compound is
attached to textiles [46].
The attachment of QAC to a textile substrate is believed
to be predominantly by ionic interaction between the cationic QAC and anionic fiber surface [47, 48]. Therefore,
for polyester fibers such as Acrilan® (from Acrilan) and
Orlon® (from Dupont) which contain carboxylic or sulfonate groups, QAC can be directly exhausted under near
boiling conditions [49, 50, 51]. Similarly, the glutamyl and
aspartyl residues in wool provide carboxylic groups.
Exhaustion of QACs, particularly cetylpyridinium chloride,
onto untreated wool at a level of around 5% oww can
render it antimicrobial with durability to 10 launderings [52,
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53]. Cotton fabrics have been treated with a 4-aminobenzenesulfonic acid-chloro-triazine adduct which increased the
anionic sites on the fabric surface and facilitated the
exhaustion of QACs [54]. In general, the exhaustion in
these studies was affected by pH, the concentration of the
QAC, temperature and exhaustion time.
Other synthetic fibers, such as Nylon 66, contain fewer
reactive sites and are quite resistant to chemical modification procedures, including antimicrobial finishing. Sun and
colleagues have hypothesized that dye molecules may act
as bridges to bind functional molecules to the fiber surface
[46]. In their studies, the fabrics were first dyed with acid
dyes before QACs were applied under alkaline conditions.
The ionic interaction between the dye molecules and the
QAC was sufficiently strong to provide a semi-durable
antimicrobial finishing [46, 47, 48].
Attempts have been made to covalently attach QAC onto
wool. Diz et al. synthesized a new QAC, N-dodecyl-aminobetaine-2-mercaptoethylamine hydrochloride (DABM) [15,
55]. DABM can react with wool by means of its thiol group,
either with cysteine-S-sulphonate residues (Bunte salts) of
sodium bisulphite pretreated wool or with the disulfide
bond of cystine wool, forming an asymmetrical disulfide
bond. Such covalent attachment of the quaternary ammonium surfactant provides antimicrobial activity [15, 55].
One commercial antimicrobial textile product using
QAC as the active agent is the BIOGUARD® produced by
AEGIS Environments. The active substance, 3-trimethoxysilylpropyldimethyloctadecyl ammonium chloride (AEM
5700, formerly known as the Dow Corning 5700 Antimicrobial Agent; see Figure 1), has a MIC of 10–100 mg/l
against Gram-positive and Gram-negative bacteria [59].
AEM 5700 is made into an aqueous solution and applied
by padding, spraying and foam finishing. Upon drying, the
non-volatile silane forms covalent bonds with the textile,
resulting in excellent durability [57]. So far, this chemical
has been commercially used on cotton, polyester and nylon
fabrics. Although little information is available on bacterial
resistance to this particular QAC, bacterial resistance to
other QACs have been widely observed [58, 59].
Figure 1 Structure of 3-(trihydroxysilyl) propyldimethyloctadecyl ammonium chloride (AEM 5700).
PHMB
PHMB (Figure 2, trade name Vantocil) is a heterodisperse
mixture of polyhexamethylene biguanides with an average
molecular weight of approximately 2500 Da. Being a
potent and broad spectrum bactericidal agent with low toxicity (MIC = 0.5–10 ppm, Arch technical information), it
has been successfully used as a disinfectant in the food
industry and in the sanitization of swimming pools [27] and
is being explored as a biocide in mouthwashes [60] and
wound dressings [61]. PHMB impairs the integrity of the
cell membrane in its action, and its activity increases on a
weight basis with increasing levels of polymerization [27].
To date, bacterial resistance to PHMB has rarely been
observed although resistance to the bisbiguanide chlorhexidine is well known [58, 59].
In 1997, Payne patented a treatment of cellulosic fibers
with PHMB in which an after-treatment with a strong
organic acid was used to increase durability as well as to
overcome fabric yellowing [62]. Payne and Yates later
extended PHMB treatment to synthetic fibers using a selfcrosslinkable resin and a catalyst [63]. PHMB can also be
directly exhausted onto cotton at room temperature and
neutral pH [8, 9], or applied in a pad–dry–cure process
[64]. Owing to its cationic nature, PHMB attachment to
cotton is believed to be through ionic as well as hydrogen
bonding [65]. The carboxyl groups on cotton fabrics that
have originated from chemical finishing are involved in
some of these interactions [66, 67]. Dyeing of cotton fabrics with reactive dyes, which introduces additional anionic
sulphonic groups in the fabric, further increases the uptake
of PHMB [66, 67], but the strong ionic bonding may
decrease the release of free PHMB and antimicrobial efficiency [68]. PHMB needs to be applied at a level of 2–4%
owf for durable finishing and 0.25–1% owf for disposable
items (Arch technical information).
Arch Chemicals has developed a special grade of PHMB,
Reputex 20®, for textile treatments [69]. Reputex® has a
higher molecular weight than Vantocil, containing an average
of 16 biguanide units in the polymer (Arch technical information). This longer polymer length not only results in
higher biocidal activity but also provides more cationic sites
per molecule for possibly stronger binding to the textile surface. Reputex® is initially applied to cotton or its blends
using exhaust or pad–dry–cure processes, and more recently
to polyester and nylon [70], under the trade name Purista®.
Figure 2 Structure of polyhexamethylene biguanide
(PHMB).
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Recent Advances in Antimicrobial Treatments of Textiles Y. Gao and R. Cranston
Triclosan
Triclosan (2,4,4’-trichloro-2’-hydroxydiphenyl ether, Figure 3)
is a broad-spectrum antimicrobial agent with a MIC of less
than 10 ppm against many common bacterial species [71].
Unlike most other cationic biocides used on textiles, triclosan
is not ionized in a solution. It has been in use since the 1960s
in a wide array of professional and consumer products
including hand soaps, surgical scrubs, shower gels, deodorants, healthcare handwashes, toothpastes and mouthwashes
[71, 72]. It inhibits microbial growth by blocking lipid biosynthesis [73].
In 2004, Payne patented the treatment of cotton or cotton blends with triclosan mixed with a polyurethane resin
and a plasticizer [74]. Being a relatively small molecule, triclosan can also act like a disperse dye and can be used by
exhaustion prior to dyeing, together with dyeing or after
dyeing of polyester and nylon fibers at 5% owf (see [7]).
During fabric use, the agent migrates to the surfaces of the
treated textiles at a slow yet sustained rate to provide antimicrobial efficacy [7]. To achieve a more durable finishing,
triclosan has been inserted into the hydrophobic cavity of
β-cyclodextrins to form an inclusion complex which was
then embedded in a polymer film or fiber [75], or encapsulated in microspheres which were subsequently attached to
viscose [76]. Triclosan can also be directly incorporated
into synthetic polymers through melt-mixing or suspension
polymerization [77, 78].
A number of companies manufacture and market triclosan-based fibers, yarns or fabrics. For instance, the nylon
and polyester products Tinosan AM 100® and CEL® (Ciba
Speciality Chemicals), the Silfresh® cellulose acetate yarn
(Novaceta) and Microban® textile products (Microban
International) all contain triclosan as the active antimicrobial agent which is applied at the finishing stage or incorporated into the fiber during extrusion [7, 10].
However, bacterial resistance to triclosan has been well
documented and is of great concern [59, 79]. Furthermore,
when exposed to sunlight in the environment, triclosan
breaks down into 2,8-dichlorodibenzo-p-dioxin [80, 81] which
is chemically related other toxic polychlorinated dioxins
[82]. Owing to such health and environmental issues, a
number of leading retailers as well as governments in
Europe are concerned about or have banned the “unneces-
Figure 3 Structure of triclosan.
65
sary use” of triclosan in textiles and some other products
[83, 84].
Chitosan
Chitosan (Figure 4) is the deacetylated derivative of chitin,
which is the main component of the shells of crustaceans
such as shrimps, crabs and lobsters [85]. Large quantities of
chitin are produced as a byproduct of the seafood industry.
Chitosan has been found to inhibit the growth of microbes
in a large body of work that has been extensively reviewed
by Lim and Hudson [86]. It has a MIC of 0.05–0.1% (w/v)
against many common bacterial species, although the activity can be affected by its molecular weight and degree of
deacetylation [86, 87, 88]. The antimicrobial mechanism is
not clear but is generally accepted that the primary amine
groups provide positive charges which interact with negatively charged residues on the surface of microbes. Such
interaction causes extensive changes in the cell surface
and cell permeability, leading to leakage of intracellular
substances [86]. This antimicrobial ability, coupled with
its non-toxicity, biodegradability and biocompatibility, is
facilitating chitosan’s emerging applications in food science, agriculture, medicine, pharmaceuticals and textiles
[85, 86].
Figure 4 Deacetylation of chitin to chitosan.
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The prime focus for chitosan as an antimicrobial treatment has been on cotton. Early work indicated that the antimicrobial effect was potent against a range of microbes, but
the finishing was not durable [86]. To improve durability,
chitosan has been crosslinked to cotton using chemicals
such as dimethyloldihydroxyethyleneurea (DMDHEU),
citric acid, 1,2,3,4-butanetetracarboxylic acid (BTCA) or
glutaric dialdehyde [16, 17, 89, 90]. These chemicals, some
of which are used in cotton durable press, crosslink chitosan
to cotton through hydroxyl groups. Antimicrobial activity
with a durability of up to 50 washes has been reported in
some of these studies. Ye et al. [12, 13] synthesized nanoscale core–shell particles of poly(n-butyl acrylate) cores and
chitosan shells and applied them to cotton fabrics in a pad–
dry–cure process. The antibacterial activity was maintained
at over 90% reduction levels after 50 washes.
Chitosan has been applied to wool as a shrink-proofing
polymer, although antimicrobial activity of the treated
wool was not examined in these studies [91, 92, 93, 94, 95,
96]. Given the intrinsic antimicrobial activity of chitosan, it
is envisaged that the shrink-proofing treatment will dually
lead to antimicrobial function. Owing to the hydrophobic
and non-reactive nature of the wool fiber surface, treatment with chitosan requires pre-treatments so that the polymer can adhere to the surface. Pre-treatments include
oxidation with peroxide [91, 92, 93], protease digestion [94,
95] and plasma treatment [96]. Hsieh et al. reported oxidizing wool with potassium permanganate and crosslinking
chitosan onto it using citric acid in a pad–dry–cure treatment [97]. Although chitosan conferred durable antimicrobial ability and shrink resistance, the disadvantage was that
the handle of the fabric, together with some other physical
properties, was adversely affected [93, 97, 98].
In addition to native chitosan, a number of chitosan
derivatives have been synthesized and used as antimicrobial
agents on textiles. These include chito-oligosaccharide [99,
100], N-(2-hydroxy)propyl-3-trimethylammonium chitosan
chloride [101, 102, 103] and N-p-(N-methylpyridinio)methylated chitosan chloride and N-4-[3-(trimethyl-ammonio)
propoxy]benzylated chitosan chloride [104]. Many of these
derivatives contain a quaternary ammonium group to enhance
the antimicrobial activity. Another derivative is O-acrylamidomethyl-N-[(2-hydroxyl-3-trimethylammonium)propyl] chitosan chloride [14]. The acrylamidomethyl group is fiber
reactive and can form a covalent bond with cellulose in cotton, resulting in excellent durability. Kenawy et al. attached
several compounds to the reactive amino group of chitosan
[105]. These modified chitosans were highly active against
microbes, in particular fungi species.
Despite such active research and recent patents covering the use of chitosan on cotton [106] and polyester [107],
chitosan has yet to be used as a finishing agent on any commercial textiles. The poor handle, among other factors,
may be limiting its application on textiles. Nevertheless,
the Swiss company Swicofil manufactures a composite
fiber of chitosan and viscose, Crabyon®, that has durable
antimicrobial efficacy and is suitable for a range of textile
products [108]. Furthermore, chitosan can be spun into fibers but their applications seem to be limited to medical
uses (e.g. medical gauzes, sutures and wound dressings)
[109, 110].
Regenerable N-halamine and Peroxyacid
One route that has been explored for durable antimicrobial finishing is to make the finishing regenerable by using
chlorine-containing N-halamine compounds. N-halamine
compounds are broad-spectrum disinfectants that have
been used in water treatment [111], and their antimicrobial
ability is attributed to the oxidative properties of the halamine bond (N–Cl). In deactivating a microorganism, the
N-halamine bond is reversibly reacted to N–H. However,
the inactive substance can be recharged with chlorine in a
bleaching solution during laundering, as depicted in Figure 5
(see also 112). This regenerable approach was first proposed and demonstrated for the treatment of cotton by
Sun and Xu in 1998 [113]. Different heterocyclic N-halamine compounds have since been covalently attached to
nylon [114], polyester fibers [115, 116], cotton [116] and
keratinous fibers [117], or grafted onto cellulosic fabrics
[18, 118, 119, 120] and synthetic fabrics [121, 122]. In most
cases strong and regenerable antimicrobial activity was
achieved by washing and recharging the substrates in aqueous solution containing chlorine.
However, as pointed out by Li [123], N-halamine treatment also results in a substantial amount of adsorbed chlorine (or other halogens) remaining on the surface of the
fabric in addition to the covalently bonded N-halamines.
Such residual adsorbed halogen (e.g. chlorine) produces
an unpleasant odor and discolors fabrics, which has proven
problematic for such a promising antimicrobial system in
the textile industry. A reduction step (i.e. with sodium
sulfite) has been used to remove the unbonded residual
Figure 5 Regenerable antimicrobial treatments using Nhalamine compounds (A) and peroxyacids (B).
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Recent Advances in Antimicrobial Treatments of Textiles Y. Gao and R. Cranston
67
Table 1 Some commercially used biocides and those under development for the treatment of various fibers. In the
application method column, “F” denotes that biocide is used as finishing agent and “I” denotes that biocide is incorporated
into the fiber during extrusion.
Application
method
Commercial
products?
Polyester
Nylon
Wool
Regenerated cellulose
F/I
I
F
F
Yes
Yes
Yes
Yes?
Slow release, durable but Ag can be depleted
QACs
(e.g. AEM
5700)
Cotton
Polyester
Nylon
Wool
F
F
F
F
Yes
Yes
Yes
No
Covalent bonding, very durable, Possible bacterial resistance
PHMB
Cotton
Polyester
Nylon
F
F
F
Yes
Yes
Yes
Large amount needed, Potential bacterial resistance
Triclosan
Polyester
Nylon
Polypropylene
Cellulose acetate
Acrylic fiber
F/I
F/I
I
I
I
Yes
Yes
Yes
Yes
Yes
Large amt needed, Bacterial resistance, breaks
down into toxic dioxin, banned in some European countries
Chitosan
Cotton
Polyester
Wool
F
F
F
No
No
No
Adverse effect on handle, low durability
N-halamine Cotton
Polyester
Nylon
Wool
F
F
F
F
No
No
No
No
Needs regeneration, odor from residual chlorine
Peroxyacids Cotton
Polyester
F
F
No
No
Needs regeneration, poor durability
Biocide
Fiber
Silver
chlorine (or other halogen) from the target fabric surface
to overcome this problem [123].
An alternative regenerable antimicrobial finishing uses
peroxyacids, such as peroxyacetic acid which is a well
known and powerful disinfectant used in hospitals [124].
Peroxyacids are converted to carboxylic acid in deactivating microbes but can be regenerated through the reaction
with an oxidant (e.g. hydrogen peroxide) [125, Figure 5].
Huang and Sun demonstrated the feasibility by grafting
BTCA or citric acid onto cotton fabrics in a pad–dry–cure
process similar to cotton durable press [125, 126]. The
grafted polycarboxylic acid provided the necessary carboxylic groups which were then converted to peroxyacids in an
oxygen bleach bath [125] or with the strong oxidant sodium
perborate [126]. Such finishing can also be applied to polyester fabrics [127]. While the peroxyacids on the fabrics
was stable over extended periods during fabric storage, the
antimicrobial activity appeared to be diminished after several washing and recharging cycles [125, 126].
Comments
Dyes
Some synthetic dyes used in the textile industry, e.g. metallic dyestuff, exhibit antimicrobial activities [128]. Therefore,
dyeing and antimicrobial finishing can be simultaneously
achieved by choosing specific dyes. Some synthetic dyes
have been specifically made with antimicrobial activity. For
examples, a new series of azo disperse dyestuffs, prepared
by the reaction of sulphanilamidodiazonium chloride
derivatives with indan-1,3-dione, gave excellent dyeing and
antimicrobial results on wool and nylon [129]. Another
approach to achieve simultaneous dyeing and antimicrobial finishing is to covalently attach a biocide to a dye via a
linker. For example, novel cationic dyes were synthesized
by linking quaternary ammonium group to the aminoanthraquinioid chromophore [130, 131]. These dyes showed
varying levels of antimicrobial activities, depending on
their structures, but when applied to acrylic fabrics the
antimicrobial durability generally did not last for more
than five washes [132]. Some natural dyes have also been
examined for antimicrobial ability. Curcumin, a common
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dye used for fabric and food colorations [133], a dye isolated from Quercus infectoria [134] and the colorant Berberine, which contains the quaternary ammonium group,
all exhibit durable antimicrobial efficacy when attached to
textiles []135.
Summary
The biocides discussed above are summarized in Table 1.
Silver, PHMB, quaternary ammonium compounds and triclosan are currently used in commercial antimicrobial textiles of synthetic fibers (e.g. nylon, polyester, cellulose
acetate or polypropylene) and natural fibers (cotton and
wool), while chitosan and a number of regenerable biocides
are in the development stage. These biocides, depending on
the particular fiber, can be used either as finishing agents or
incorporated into the fiber during extrusion.
microbial textiles should be considered and monitored
closely.
Acknowledgment
The authors would like to offer their sincere thanks to Dr
David J. Evans and Dr Ron J. Denning, Division of Textile
and Fibre Technology, CSIRO, for critically reading the
manuscript during its preparation.
Literature Cited
1.
2.
3.
Conclusion
Customer desire for comfort, hygiene and well-being has
created a large and rapidly increasing market for antimicrobial textiles. Numerous manufacturers in the textile industry have responded to this demand by launching their brands
of antimicrobial products. These products use broad-spectrum biocides such as silver, polyhexamethylene biguanide,
quaternary ammonium compounds and triclosan as the
active agents. Some treatments are applied at the finishing
stage while in other cases the biocide can be incorporated
into synthetic fibers during extrusion. Collectively, commercial antimicrobial textiles cover most of the major fiber
types in the textile industry. On the other hand, the use of
several other biocides, such as chitosan and its derivatives,
specific dyes and regenerable active N-halamine compounds
and peroxyacids, is in the development stage. These products vary in their effectiveness and durability depending on
the type of fabric, the biocide and the finishing method used
in the system. In some cases the antimicrobial efficacy is lost
or severely depleted after 10 or fewer washing cycles.
While antimicrobial textiles provide the benefits in
hygiene, odor control and protection of the fabric from
microbial attack, bacterial resistance to the biocides used
and their toxic breakdown products in the household and
environment have been concerns. Most biocides used on
commercial textiles can induce bacterial resistance to these
substances, which can lead to increased resistance to certain antibiotics in clinical use [136]. Bacterial resistance
may be a particular concern because large quantities of
biocides are needed on the textiles to achieve adequate
activity and durability. Such concerns have resulted in the
banning of the use of triclosan on textiles by a number
leading retailers and governments in Europe. The longterm benefits and potential problems associated with anti-
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Purwar, R., and Joshi, M., Recent Developments in Antimicrobial Finishing of Textiles—A Review, AATCC Review, 4,
22–26 (2004).
The 2nd European Conference on Textiles and the Skin, Bönnigheim, Germany 2004, http://www.hohenstein.com.tr/ximages/15676_hohtextile.pdf (accessed June 2007).
Pavlidou, V., New Multifunctional Textiles: Antimicrobial
Treatments, in “Proceedings of the Intelligent Textile Structures—Application, Production and Testing International
Workshop”, Thessaloniki, Greece 2005, http://centrum.vslib.
cz/centrum/itsapt/greece2005.html (accessed June 2007).
Antimicrobial Fabrics Help Fight War Against Germs, http://
www.textilesintelligence.com/til/press.cfm?prid=325
(accessed June 2007).
Williams, J. F., HaloSource, V., and Cho, U., Antimicrobial
Functions for Synthetic Fibers: Recent Developments,
AATCC Review, 5, 17–21 (2005).
Elsner, P., Antimicrobials and the Skin Physiological and
Pathological Flora, in “Biofunctional Textiles and the Skin,”
Hipler, U. C., and Elsner, P. (eds), Karger, Basel, 2006, pp. 3541.
Mao, J. W., and Murphy, L., Durable Freshness for Textiles,
AATCC Review, 1, 28–31 (2001).
Payne, J. D., and Kudner, D. W., A Durable Antiodor Finish
for Cotton Textiles, Textile Chemist and Colorist 28, 28–30
(1996).
Wallace, M. L., Testing the Efficacy of Polyhexamethylene
Biguanide as an Antimicrobial Treatment for Cotton Fabric,
AATCC Review, 1, 18–20 (2001).
Mansfield, R. G., Keeping it Fresh, Textile World, 152, 42–45
(2002).
Lee, H. J., Yeo, S. Y, and Jeong, S. H., Antibacterial Effect of
Nanosized Silver Colloidal Solution on Textile Fabrics, J.
Mater. Sci., 38, 2199–2204 (2003).
Ye, W. J. et al., Novel Core–Shell Particles with Poly(n-butyl
acrylate) Cores and Chitosan Shells as an Antibacterial Coating for Textiles, Polymer, 46, 10538–10543 (2005).
Ye, W. J. et al., Durable Antibacterial Finish on Cotton Fabric
by using Chitosan-based Polymeric Core–Shell Particles, J.
Appl. Polymer Sci., 102, 1787–1793 (2006).
Lim, S. H., and Hudson, S. M., Application of a Fiber-reactive
Chitosan Derivative to Cotton Fabric as an Antimicrobial Textile Finish, Carbohydr. Polymer, 56, 227–234 (2004).
Diz, M., Jocic, D., Infante, M. R., and Erra, P., Reaction of a
New Thiol Cationic Surfactant with Bunte Salt in Wool Fibers, Textil. Res. J., 67, 486–493 (1997).
Downloaded from http://trj.sagepub.com at MICHIGAN STATE UNIV LIBRARIES on March 6, 2008
© 2008 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Recent Advances in Antimicrobial Treatments of Textiles Y. Gao and R. Cranston
16. El-Tahlawy, K. F., El-Bendary, M. A., Elhendawy, A. G., and
Hudson, S. M., The Antimicrobial Activity of Cotton Fabrics
Treated with Different Crosslinking Agents and Chitosan,
Carbohydr. Polymer, 60, 421–430 (2005).
17. Zhang, Z. T., Chen, L., Ji, J. M., Huang, Y. L., and Chen, D.
H., Antibacterial Properties of Cotton Fabrics Treated with
Chitosan, Textil. Res. J., 73, 1103–1106 (2003).
18. Sun, Y., and Sun, G., Durable and Regenerable Antimicrobial
Textile Materials Prepared by a Continuous Grafting Process,
J. Appl. Polymer Sci., 84, 1592–1599 (2002).
19. Attia, S. M. et al., Review on Sol-gel Derived Coatings: Process, Techniques and Optical Applications, J. Mater. Sci. Technol., 18, 211–218 (2002).
20. Mahltig, B., Haufe, H., and Bottcher, H., Functionalisation of
Textiles by Inorganic Sol-gel Coatings, J. Mater. Chem., 15,
4385–4398 (2005).
21. Cunko, R., and Varga, K., Application of Ceramics for the
Production of High-performance Textiles, TEKSTIL, 55, 267–
278 (2006).
22. Mahltig, B., Fiedler, D., and Bottcher, H., Antimicrobial Solgel Coatings, J. Sol-Gel Sci. Technol., 32, 219–222 (2004).
23. Joiner, B. G., Determining Antimicrobial Efficacy and Biocompatibility of Treated Articles using Standard Test Methods, in “Bioactive Fibres and Polymers”, Edwards, J. V., and
Vigo, T. L. (eds), American Chemical Society, Washington
DC, 2001, Ch. 12, pp. 201–217.
24. Hofer, D., Antimicrobial Textiles—Evaluation of their Effectiveness and Safety, in “Biofunctional Textiles and the Skin”,
Hipler, U. C., and Elsner, P. (eds), Karger, Basel, 2006,
pp. 42–50.
25. Analysis and Assessment of Current Protocols to Develop Harmonised Test Methods and Relevant Performance Standards for
the Efficacy Testing of Treated Articles/Treated Materials, http://
www.olis.oecd.org/olis/2007doc.nsf/43bb6130e5e86e5fc12569
fa005d004c/0b18528d8e9cec03c1257288005b024c/$FILE/
JT03222464.PDF (accessed June 2007).
26. Determination of Antibacterial Activity of Antibacterial
Finished Products, http://www.iso.org/iso/en/CatalogueDetailPage.CatalogueDetail?CSNUMBER=34261&scopelist=
PROGRAMME (accessed June 2007).
27. McDonnell, G., and Russell, A. D., Antiseptics and Disinfectants: Activity, Action, and Resistance, Clin. Microbiol. Rev.,
12, 147–179 (1999).
28. http://www.cupron.com/Cupron-News-Antimicrobial/.
29. Yadav, A. et al., Functional Finishing in Cotton Fabrics using
Zinc Oxide Nanoparticles, Bull. Mater. Sci., 29, 641–645 (2006).
30. Charbonneaux, T., and Rochat, S., “Articles with Antibacterial
and Antifungal Activity”, United States Patent Application
20060208390 (2006).
31. Antelman, M. S., “High Performance Cobalt (II,III) Oxide
Antimicrobial Textile Articles”, United States Patent no
6,228,491 (2001).
32. Hermans, M. H., Silver-containing Dressings and the Need
for Evidence, Am. J. Nurs., 106, 60–68 (2006).
33. Butkus, M. A., Edling, L., and Labare, M. P., The Efficacy of
Silver as a Bactericidal Agent: Advantages, Limitations and
Considerations for Future Use, J. Water Sup. Res. Tech.-Aqua,
52, 407–416 (2003).
34. Percival, S. L., Bowler, P. G., and Russell, D., Bacterial Resistance to Silver in Wound Care, J. Hosp. Infect., 60, 1–7 (2005).
69
35. Silver, S., and Phung le, T., Silver, G., Silver as biocides in
burn and wound dressings and bacterial resistance to silver
compounds, J. Ind. Microbiol. Biotechnol. 33, 627-634. (2006).
36. Yeo, S. Y., Lee, H. J., and Jeong, S. H., Preparation of Nanocomposite Fibers for Permanent Antibacterial Effect, J. Mater.
Sci., 38, 2143–2147 (2003).
37. Son, W. K., Youk, J. H., and Park, W. H., Antimicrobial Cellulose Acetate Nanofibers Containing Silver Nanoparticles,
Carbohydr. Polymer, 65, 430–434 (2006).
38. Hong, K. H., Park, J. L., Sul, I. H., Youk, J. H., and Kang, T. J.,
Preparation of Antimicrobial Poly(vinyl alcohol) Nanofibers
Containing Silver Nanoparticles, J. Polymer Sci. B Polymer
Phys., 44, 2468–2474 (2006).
39. Hipler, U.C., Elsner, P., and Fluhr, J.W., Antifungal and Antibacterial Properties of a Silver-loaded Cellulosic Fiber, J.
Biomed. Mater. Res. B Appl. Biomater., 77, 156–163 (2006).
40. Nakashima, T., Sakagami, Y., Ito, H., and Matsuo, M., Antibacterial Activity of Cellulose Fabrics Modified with Metallic
Salts, Textil. Res. J., 71, 688–694 (2001).
41. Freddi, G., Arai, T., Colonna, G. M., Boschi, A., and Tsukada,
M., Binding of Metal Cations to Chemically Modified Wool
and Antimicrobial Properties of the Wool–Metal Complexes,
J. Appl. Polymer Sci., 82, 3513–3519 (2001).
42. Arai, T., Freddi, G., Colonna, G. M., Scotti, E., Boschi, A.,
Murakami, R., and Tsukada, M., Absorption of Metal Cations
by Modified B-mori Silk and Preparation of Fabrics with an
Antimicrobial Activity, J. Appl. Polymer Sci., 80, 297–303 (2001).
43. Tsukada, M., Arai, T., Colonna, G. M., Boschi, A., and Freddi,
G., Preparation of Metal-containing Protein Fibers and their
Antimicrobial Properties, J. Appl. Polymer Sci., 89, 638–644
(2003).
44. The AgION® Technology Behind the Performance, http://
www.bioshieldtech.com/tech.html (accessed June 2007).
45. NanoHorizons Announces SmartSilver Anti-Odor Nanotechnology for Wool, http://www.azonano.com/news.asp?newsID=
3609 (accessed June 2007).
46. Kim, Y. H., and Sun, G., Dye Molecules as Bridges for Functional Modifications of Nylon: Antimicrobial Functions, Textil.
Res. J., 70, 728–733 (2000).
47. Kim, Y. H., and Sun, G., Durable Antimicrobial Finishing of
Nylon Fabrics with Acid Dyes and a Quaternary Ammonium
Salt, Textil. Res. J., 71, 318–323 (2001).
48. Son, Y. A., and Sun, G., Durable Antimicrobial Nylon 66 Fabrics: Ionic Interactions with Quaternary Ammonium Salts, J.
Appl. Polymer Sci., 90, 2194–2199 (2003).
49. Kim, Y. H., and Sun, G., Functional Finishing of Acrylic and
Cationic Dyeable Fabrics: Intermolecular Interactions, Textil.
Res. J., 72, 1052–1056 (2002).
50. Cai, Z. S., and Sun, G., Antimicrobial Finishing of Acrilan
Fabrics with Cetylpyridinium Chloride, J. Appl. Polymer Sci.,
94, 243–247 (2004).
51. Cai, Z. S., and Sun, G., Antimicrobial Finishing of Acrilan
Fabrics with Cetylpyridinium Chloride: Affected Properties
and Structures, J. Appl. Polymer Sci., 97, 1227–1236 (2005).
52. Zhu, P., and Sun, G., Antimicrobial Finishing of Wool Fabrics
using Quaternary Ammonium Salts, J. Appl. Polymer Sci., 93,
1037–1041 (2004).
53. Zhao, T., and Sun, G., Antimicrobial Finishing of Wool Fabrics with Quaternary Aminopyridinium Salts, J. Appl. Polymer
Sci., 103, 482–486 (2006).
Downloaded from http://trj.sagepub.com at MICHIGAN STATE UNIV LIBRARIES on March 6, 2008
© 2008 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
TRJ
TRJ
70
Textile Research Journal 78(1)
54. Son, Y. A., Kim, B. S., Ravikumar, K., and Lee, S. G., Imparting Durable Antimicrobial Properties to Cotton Fabrics using
Quaternary Ammonium Salts through 4-Aminobenzenesulfonic Acid-chloro-triazine Adduct, Eur. Polymer J., 42, 3059–
3067 (2006).
55. Diz, M., Infante, M. R., Erra, P., and Manresa, A., Antimicrobial Activity of Wool Treated with a New Thiol Cationic Surfactant, Textil. Res. J., 71, 695–700 (2001).
56. Hayes, S. F., and White, W. C., How Antimicrobial Treatment
can Improve Nonwovens, http://www.aegisasia.com/How_Antimicrobial_Treatment_Can_Improve.pdf (accessed June 2007).
57. A New, Durable Antimicrobial Finish for Textiles, http://
microbeshield.com/techdocs/
New_Durable_Antimicrobial_Finish_for_Textiles_4A1-F.pdf
(accessed June 2007).
58. Russell, A. D., Introduction of Biocides into Clinical Practice
and the Impact on Antibiotic Resistance, J. Appl. Microbiol.
92, 121S–135S (2002).
59. Russell, A. D., Bacterial Adaptation and Resistance to Antiseptics, Disinfectants and Preservatives is Not a New Phenomenon, J. Hosp. Infect., 57, 97–104 (2004).
60. Rosin, M., Welk, A., Bernhardt, O., Ruhnau, M., Pitten, F. A.,
Kocher, T., and Kramer, A., Effect of a Polyhexamethylene
Biguanide Mouthrinse on Bacterial Counts and Plaque, J.
Clin. Periodontol., 28, 1121–1126 (2001).
61. Cazzaniga, A., Serralta, V., Davis, S., Orr, R., Eaglstein, W.,
and Mertz, P. M., The Effect of an Antimicrobial Gauze
Dressing Impregnated with 0.2-percent Polyhexamethylene
Biguanide as a Barrier to Prevent Pseudomonas aeruginosa
Wound Invasion, Wound-compend. Clin. Res. Prac., 14, 169–
176 (2002).
62. Payne, J. D., “Antimicrobial Treatment of Textile Materials”,
United States Patent no 5,700,742, (1997).
63. Payne, J. D., and Yates, J. E., “Fibres Treated with Antimicrobial Agents”, European Patent Office Publication no
EP1697577(A1) (2006).
64. Yang, Y. Q., Corcoran, L., Vorlicek, K., and Li, S., Durability
of Some Antibacterial Treatments to Repeated Home Launderings, Textile Chemist and Colorist Am. Dyestuff Rep., 32, 44–
49 (2000).
65. Blackburn, R. S. et al., Sorption of Poly(hexamethylenebiguanide) on Cellulose: Mechanism of Binding and Molecular
Recognition, Langmuir, 22, 5636–5644 (2006).
66. Kawabata, A., and Taylor, J. A., Effect of Reactive Dyes upon
the Uptake and Antibacterial Action of Poly(hexamethylene
biguanide) on Cotton. Part 1: Effect of Bis(monochlorotriazinyl) Dyes, Color. Technol., 120, 213–219 (2004).
67. Kawabata, A., and Taylor, J. A., The Effect of Reactive Dyes
upon the Uptake and Antibacterial Action of Poly(hexamethylene biguanide) on Cotton. Part 2: Uptake of Poly(hexamethylene
biguanide) on Cotton Dyed with Beta-sulphatoethylsulphonyl
Reactive Dyes, Dyes Pigments, 68, 197–204 (2006).
68. Kawabata, A., and Taylor, J. A., The Effect of Reactive Dyes
upon the Uptake and Antibacterial Action of Poly(hexamethylene biguanide) on Cotton. Part 3: Reduction in the Antibacterial Efficacy of Poly(hexamethylene biguanide) on Cotton,
Dyed with Bis(monochlorotriazinyl) Reactive Dyes, Carbohydr. Res., 67, 375–389 (2007).
69. http://www.archchemicals.com/Fed/BIO/Products/Brand/reputex. htm (accessed June 2007).
70. Purista to Develop Freshness Treatment for Synthetic Fibres,
http://www.fibre2fashion.com/news/company-news/purista/
newsdetails.aspx?news_id=22045 (accessed June 2007).
71. Jones, R. D., Jampani, H. B., Newman, J. L., and Lee, A. S.,
Triclosan: A Review of Effectiveness and Safety in Health
Care Settings, Am. J. Infect. Contr., 28, 184–196 (2000).
72. Bhargava, H. N., and Leonard, P. A., Triclosan: Applications
and Safety, Am. J. Infect. Contr., 24, 209-218 (1996).
73. Levy, C. W., Roujeinikova, A., Sedelnikova, S., Baker, P. J.,
Stuitje, A. R., Slabas, A. R., Rice, D. W., and Rafferty, J. B.,
Molecular Basis of Triclosan Activity, Nature, 398, 383–384
(1999).
74. Payne, S. A., “Antimicrobial Superfinish and Method of Making”, United States Patent Application no 20040077747 (2004).
75. Lu, J., Hill, M. A., Hood, M., Greeson, D. F., Horton, J. R.,
Orndorff, P. E., Herndon, A. S., and Tonelli, A.E., Formation
of Antibiotic, Biodegradable Polymers by Processing with
Irgasan DP300R (Triclosan) and its Inclusion Compound with
Beta-cyclodextrin, J. Appl. Polymer Sci., 82, 300–309 (2001).
76. Goetzendorf-Grabowska, B., Krolikowska, H., and Gadzinowski, M., Polymer Microspheres as Carriers of Antibacterial Properties of Textiles: A Preliminary Study, Fibres and
Textiles in Eastern Europe, 12, 62–64 (2004).
77. Kalyon, B. D., and Olgun, U., Antibacterial Efficacy of Triclosan-incorporated Polymers, Am. J. Infect. Contr., 29, 124–
125 (2001).
78. Iconomopoulou, S. M., Andreopoulou, A. K., Soto, A., Kallitsis, J. K., and Voyiatzis, G. A., Incorporation of Low Molecular Weight Biocides into Polystyrene-divinyl Benzene Beads
with Controlled Release Characteristics, J. Contr. Release, 102,
223–233 (2005).
79. Yazdankhah, S. P. et al., Triclosan and Antimicrobial Resistance in Bacteria: An Overview, Microb. Drug Resist.-Mech.
Epidemiol. Dis., 12, 83–90 (2006).
80. Latch, D. E. et al., Photochemical Conversion of Triclosan to
2,8-Dichlorodibenzo-p-dioxin in Aqueous Solution, J. Photchem. Photobiol. Chem., 158, 63–66 (2003).
81. Sanchez-Prado, L. et al., Further Research on the PhotoSPME of Triclosan, Anal. Bioanal. Chem., 384, 1548–1557
(2006).
82. Larsen, J. C., Risk Assessments of Polychlorinated Dibenzop-dioxins, Polychlorinated Dibenzofurans, and Dioxin-like
Polychlorinated Biphenyls in Food, Mol. Nutr. Food Res., 50,
885–896 (2006).
83. Why We Do Not Use Microban®, http://www.cleanshopper.com/microban.php (accessed June 2007).
84. Triclosan, Banned from UK supermarkets, http://www.annieappleseedproject.org/tricbanfromu.html (accessed June 2007).
85. Rinaudo, M., Chitin and Chitosan: Properties and Applications, Progr. Polymer Sci., 31, 603–632 (2006).
86. Lim, S. H., and Hudson, S. M., Review of Chitosan and its
Derivatives as Antimicrobial Agents and Their uses as Textile
Chemicals, J. Macromol. Sci. Polymer Rev., 43, 223–269 (2003).
87. No, H. K., Park, N. Y., Lee, S. H., and Meyers, S. P., Antibacterial Activity of Chitosans and Chitosan Oligomers with Different Molecular Weights, Int. J. Food Microbiol., 74, 65–72
(2002).
88. Shin, Y., Yoo, D. I., and Jang, J., Molecular Weight Effect on
Antimicrobial Activity of Chitosan Treated Cotton Fabrics, J.
Appl. Polymer Sci., 80, 2495–2501 (2001).
Downloaded from http://trj.sagepub.com at MICHIGAN STATE UNIV LIBRARIES on March 6, 2008
© 2008 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Recent Advances in Antimicrobial Treatments of Textiles Y. Gao and R. Cranston
89. Lee, S., Cho, J. S., and Cho, G. S., Antimicrobial and Blood
Repellent Finishes for Cotton and Nonwoven Fabrics based
on Chitosan and Fluoropolymers, Textil. Res. J., 69, 104–112
(1999).
90. Chung, Y. S., Lee, K. K., and Kim, J. W., Durable Press and
Antimicrobial Finishing of Cotton Fabrics with a Citric Acid
and Chitosan Treatment, Textil. Res. J., 68, 772–775 (1998).
91. Julia, M. R., Cot, M., Erra, P., Jocic, D., and Canal, J. M., The
Use of Chitosan on Hydrogen Peroxide Pretreated Wool, Textile Chemist and Colorist, 30, 78–83 (1998).
92. Pascual, E., and Julia, M. R., The Role of Chitosan in Wool
Finishing, J. Biotechnol., 89, 289–296 (2001).
93. Roberts, G. A. F., and Wood, F. A., A Study of the Influence
of Structure on the Effectiveness of Chitosan as an Anti-felting Treatment for Wool, J. Biotechnol., 89, 297–304 (2001).
94. Rybicki, E., Filipowska, B., and Walawska, A., Application of
Natural Biopolymers in Shrink-proofing of Wool, Fibres and
Textiles in Eastern Europe, 8, 62–65 (2000).
95. Onar, N., and Sariisik, M., Application of Enzymes and Chitosan Biopolymer to the Antifelting Finishing Process, J. Appl.
Polymer Sci., 93, 2903–2908 (2004).
96. Erra, P., Molina, R., Jocic, D., Julia, M. R., Cuesta, A., and
Tascon, J. M. D., Shrinkage Properties of Wool Treated with
Low Temperature Plasma and Chitosan Biopolymer, Textil.
Res. J., 69, 811–815 (1999).
97. Hsieh, S. H., Huang, Z. K., Huang, Z. Z., and Tseng, Z. S.,
Antimicrobial and Physical Properties of Woolen Fabrics
Cured with Citric Acid and Chitosan, J. Appl. Polymer Sci., 94,
1999–2007 (2004).
98. Jeong, Y. J. et al., Changes in the Mechanical Properties of
Chitosan-treated Wool Fabric, Textil. Res. J., 72, 70–76 (2002).
99. Seong, H. S., Whang, H. S., and Ko, S. W., Synthesis of a Quaternary Ammonium Derivative of Chito-oligosaccharide as
Antimicrobial Agent for Cellulosic Fibers, J. Appl. Polymer
Sci., 76, 2009–2015 (2000).
100.Kim, J. Y., Lee, J. K., Lee, T. S., and Park, W. H., Synthesis of
Chitooligosaccharide Derivative with Quaternary Ammonium
Group and its Antimicrobial Activity against Streptococcus
mutans, Int. J. Biol. Macromol., 32, 23–27 (2003).
101.Kim, Y. H., Choi, H. M., and Yoon, J. H., Synthesis of a Quaternary Ammonium Derivative of Chitosan and its Application to a Cotton Antimicrobial Finish, Textil. Res. J., 68, 428–
434 (1998).
102.Kim, Y. H., Nam, C. W., Choi, J. W., and Jang, J. H., Durable
Antimicrobial Treatment of Cotton Fabrics using N-(2hydroxy)propyl-3-trimethylammonium Chitosan Chloride and
Polycarboxylic Acids, J. Appl. Polymer Sci., 88, 1567–1572 (2003).
103.Montazer, M., and Afjeh, M. G., Simultaneous X-linking and
Antimicrobial Finishing of Cotton Fabric, J. Appl. Polymer
Sci., 103, 178–185 (2007).
104.Suzuki, K., Oda, D., Shinobu, T., Saimoto, H., and Shigemasa,
Y., New Selectively N-substituted Quaternary Ammonium
Chitosan Derivatives, Polymer J., 32, 334–338 (2000).
105.Kenawy, E. R., Abdel-Hay, F. I., Abou El-Magd, A., and Mahmoud, Y., Biologically Active Polymers: Modification and
Anti-microbial Activity of Chitosan Derivatives, J. Bioact.
Comp. Poly. 20, 95–111 (2005).
106.Liang, C., “Anti-microbial Chitosan Composition for Textile
Products”, United States Patent Application no 20060008515
(2005).
71
107.Joerger, M. C., Koniz, R. F., Sabesan, S., and Pennias, J.,
“Antimicrobial Polyester-containing Articles and Process for
their Preparation”, United States Patent 7,081,139 (2006).
108.CRABYON®, A Fibre with Crab’s Pulp, http://www.swicofil.com/products/055chitosan.html (accessed June 2007).
109.Illarionova, E. L. et al., Fibre, Film, and Porous Materials
based on Chitosan, Fibre Chem., 27, 392–396 (1995).
110.Rathke, T. D., and Hudson, S. M., Review of Chitin and Chitosan as Fiber and Film Formers, J. Macromol. Sci. Rev. Macromol. Chem. Phys., C34, 375–437 (1994).
111.Worley, S. D., and Williams, D. E., Halamine Water Disinfectants, CRC Crit. Rev. Environ. Contr., 18, 133–175 (1988).
112.Sun, G., Durable and Regenerable Antimicrobial Textiles, in
“Bioactive Fibres and Polymers”, Edwards, J. V., and Vigo, T.
L. (eds), American Chemical Society, Washington, DC, 2001,
Ch. 14, pp. 243–252.
113.Sun. G., and Xu, X. J., Durable and Regenerable Antibacterial Finishing of Fabrics: Biocidal Properties, Textile Chemist
and Colorist, 30, 26–30 (1998).
114.Lin, J., Winkelman, C., Worley, S. D., Broughton, R. M., and
Williams, J. F., Antimicrobial Treatment of Nylon, J. Appl. Polymer Sci., 81, 943–947 (2001).
115.Lin, J., Winkelmann, C., Worley, S. D., Kim, J. H., Wei, C. I.,
Cho, U. C., Broughton, R. M., Santiago, J. I., and Williams, J.
F., Biocidal Polyester, J. Appl. Polymer Sci., 85, 177–182
(2002).
116.Sun, G., and Xu, X., “Durable and Regenerable Microbiocidal Textiles”, United States Patent no 5,882,357 (1999).
117.Wu, F. C., “Regenerable Antimicrobial Animal Fiber Materials”, United States Patent Application no 20020123281
(2002).
118.Qian, L., and Sun, G., Durable and Regenerable Antimicrobial Textiles: Improving Efficacy and Durability of Biocidal
Functions, J. Appl. Polymer Sci., 91, 2588–2593 (2004).
119.Luo, J., and Sun, Y. Y., Acyclic N-halamine-based Fibrous
Materials: Preparation, Characterization, and Biocidal Functions, J. Polymer Sci. Polymer Chem., 44, 3588–3600 (2006).
120.Liu, S., and Sun, G., Durable and Regenerable Biocidal Polymers: Acyclic N-halamine Cotton Cellulose, Ind. Eng. Chem.
Res., 45, 6477–6482 (2006).
121.Sun, Y. Y., and Sun, G., Novel Regenerable N-halamine Polymeric Biocides. III. Grafting Hydantoin-containing Monomers onto Synthetic Fabrics, J. Appl. Polymer Sci., 81, 1517–
1525 (2001).
122.Sun, Y. Y., and Sun, G., Novel Refreshable N-halamine Polymeric Biocides: Grafting Hydantoin-containing Monomers
onto High Performance Fibers by a Continuous Process, J.
Appl. Polymer Sci., 88, 1032–1039 (2003).
123.Li, S., “Method of Retaining Antimicrobial Properties on a
Halamine-treated Textile Substrate while Simultaneously
Reducing Deleterious Odor and Skin Irritation Effects”,
United States Patent no 6,576,154 (2003).
124.Dettenkofer, M., and Block, C., Hospital Disinfection: Efficacy and Safety Issues, Curr. Opin. Infect. Dis., 18, 320–325
(2005).
125.Huang, L. K., and Sun, G., Durable and Regenerable Antimicrobial Cellulose with Oxygen Bleach: Concept Proofing,
AATCC Review, 3, 17–21 (2003).
126.Huang, L. K., and Sun, G., Durable and Oxygen Bleach
Rechargeable Antimicrobial Cellulose: Sodium Perborate as
Downloaded from http://trj.sagepub.com at MICHIGAN STATE UNIV LIBRARIES on March 6, 2008
© 2008 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
TRJ
TRJ
72
Textile Research Journal 78(1)
an Activating and Recharging Agent, Ind. Eng. Chem. Res., 42,
5417–5422 (2003).
127.Sun, G., and Huang, L. K., “Regenerable Antimicrobial Polymers and Fibers with Oxygen Bleaches”, United States Patent
no 6,962,608 (2005).
128.Tsukada, M., Katoh, H., Wilson, D., Shin, B. S., Arai, T.,
Murakami, R., and Freddi, G., Production of Antimicrobially
Active Silk Proteins by Use of Metal-containing Dyestuffs, J.
Appl. Polymer Sci., 86, 1181–1188 (2002).
129.Sayed, A. Z., and El-Gaby, M. S. A., Synthesis of Novel Dyestuffs Containing Sulphonamido Moieties and Their Application on Wool and Polyamide Fibres, Color. Technol., 117, 293–
297 (2001).
130.Ma, M. H., Sun, Y. Y., and Sun, G., Antimicrobial Cationic
Dyes. Part 1: Synthesis and Characterization, Dyes Pigments,
58, 27–35 (2003).
131.Sun, G., and Ma, M., “Multifunctional Antimicrobial Dyes”,
United States Patent Application no 20050011012 (2005).
132.Ma, M. H., and Sun, G., Antimicrobial Cationic Dyes. Part 3:
Simultaneous Dyeing and Antimicrobial Finishing of Acrylic
Fabrics, Dyes Pigments, 66, 33–41 (2005).
133.Han, S. Y., and Yang, Y., Antimicrobial Activity of Wool Fabric Treated with Curcumin, Dyes Pigments, 64, 157–161 (2005).
134.Singh, R., Jain, A., Panwar, S., Gupta, D., and Khare, S. K.,
Antimicrobial Activity of Some Natural Dyes, Dyes Pigments,
66, 99–102 (2005).
135.Kim, T. K., and Son, Y. A., Effect of Reactive Anionic Agent
on Dyeing of Cellulosic Fibers with a Berberine Colorant—
Part 2: Anionic Agent Treatment and Antimicrobial Activity
of a Berberine Dyeing, Dyes Pigments, 64, 85–89 (2005).
136.Russell, A. D., Biocide Usage and Antibiotic Resistance: The
Relevance of Laboratory Findings to Clinical and Environmental Situations, Lancet Infect. Dis., 3, 794–803 (2003).
Downloaded from http://trj.sagepub.com at MICHIGAN STATE UNIV LIBRARIES on March 6, 2008
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