Professional Documents
Culture Documents
PUSHPA BAJAJ
Department of Textile Technology, Indian Institute of Technology, New Delhi 110 016, India
Key words: durable press finishes; formaldehyde; free finishes; softeners; bioprocess-
ing; breathable coatings; antimicrobial finishes; silk-like polyester.
INTRODUCTION finishes for cotton. The major factors that will act
as a driving force for change in the chemical fin-
In the past five decades, extensive work has been ishing for cotton in the next decade are the fol-
performed with the aim of developing new textile lowing:
products using new fibers, fiber blends, as well as
treating textiles with chemical finishes to impart ● The need for better quality and higher added
specific functional properties in addition to im- value chemical finishes for cotton
proving their aesthetic values. ● More environment-friendly chemical finishes
Many investigations1– 4 have been reported and application methods
which were designed to achieve a better under- ● Increased possibility of process integration to
standing of the mechanisms by which the various minimize the use of water and energy
finishes act, and to replace the empirical ap- ● Increased levels of process control, monitor-
proaches with those developed by systematic ing, and automation in textile finishing ma-
studies. chinery.
Today, with increasing awareness of environ-
mental concerns, a significant amount of legisla- In addition to the ecofriendly finishes, signifi-
tion on ecotoxicological considerations has been cant changes in the application methods have also
introduced.5–7 It is related to such important is- been made. The major treatment methods cur-
sues as health and safety during storage, appli- rently practiced for producing durable press cot-
cation and use, and safe disposal of chemicals into ton and other textiles are: pre-cure, garment dip
landfills, into water, or release in air during treatment, vapor phase, low wet pick (kiss roll
chemical processing of textiles. These have im- technique), post-cure, spray application and lam-
posed changes in chemical finishes and finishing ination, coating and lamination technology, foam
methods. So, integrated pollution control would finishing; and low pressure plasma technology.
continue for developing ecofriendly processes as In this report, a comprehensive review of var-
we approach the next millennium. ious finishing agents leading to wrinkle-free fab-
Holme8 has indicated the challenges faced, and rics with good and soft handle, breathable fabrics,
accordingly the changes required in functional antimicrobial textiles, etc., is given. Develop-
ments in bioprocessing, silk-like polyester, and
Journal of Applied Polymer Science, Vol. 83, 631– 659 (2002)
various other emerging technologies have also
© 2002 John Wiley & Sons, Inc. been highlighted.
631
632 BAJAJ
DURABLE PRESS FINISHES FOR COTTON on the lightfastness of cotton dyed with direct and
reactive dyes. In DMDHEU, it is assumed that all
Wrinkle-free cotton fabrics continue to dominate the four reactive groups combine with cellulosic
the market and are gaining universal acceptance. hydroxyl groups (Fig. 1), but the 4,5-dihydroxy
N,N-dimethylol 4,5-dihydroxyethylene urea ethylene ureas also undergo a chemical change
(DMDHEU) has been accepted as an easy-care and convert to hydantoins which are responsible
finishing agent. It exhibits high acid hydrolytic for the increased chlorine retention of the
stability and relatively low reactivity, whereas crosslinked cellulose, because the free NOC
N,N-dimethylol ethylene urea (DMEU) possesses groups combine readily with chlorine.
high reactivity and only limited hydrolytic stabil- Normally, crosslinking of cellulose with these
ity. The structure and reactivity of various meth- dimethylol compounds takes place in the presence
ylol derivatives1,9,10 as crosslinking agents is of acid-liberating catalysts, e.g., magnesium chlo-
showninTableI.Bis(hydroxymethyl)orbis(alkoxy- ride, zinc chloride, or nitrate by the pad-dry-cure
methyl) derivatives of carbamates have also been method. Crosslinking occurs within the accessible
used for easy-care finishing of cotton. Interest- regions with hydroxyl groups. Intermolecular
ingly, there is a direct correlation between the crosslinking provides an increase in the fiber re-
hydrolytic stability of the reactant and its effect sistance to deformation and improved elastic re-
FINISHING OF TEXTILE MATERIALS 633
urea, natural shellac, chitosan, TEA.HCl, and on N,N-dimethyl, 4,5 dihydroxyethylene urea
EDTA along with DMDHEU has been studied. (DMeDHEU). This is a zero-formaldehyde-based
Formaldehyde release was minimal in TEA.HCl crosslinking agent for cotton that crosslinks
(Figs. 4 and 5). By these methods, it has been through the ring hydroxyl groups of cellulose.
possible to limit the formaldehyde release.20,21 However, such derivatives are more expensive
However, in the 1990s, the quest has been to and somewhat less effective than DMDHEU at
search for zero formaldehyde-based reactants for the same add-on level, possibly through hydan-
cotton that will provide a low-cost efficient alter-
native to the products derived from N-hydroxy-
Table IV Thresholds for Formaldehyde in the
methyl derivatives. One approach has been to use
Workplace (Status 1996)
glyoxal urea-based derivatives such as that based
Country Thresholds (ppm)
Glyoxal
Cotton on treatment with glyoxal in the presence
of an acid catalyst such as boric acid or ammo-
nium chloride and aluminum sulphate on heating
gives monoacetals and diacetals of glyoxal with
cellulose (Fig. 6).
Free aldehyde groups present because of sin-
gle-ended attachment of glyoxal as in (I) were
found to be removable by oxidation with chlorous
acid or reduction with potassium borohydride. Be- Figure 6 Reaction of Glyoxal with cellulose.
636 BAJAJ
fabric yellowing and severe fabric strength losses. ther process improvement consists of adding a
The use of aluminum sulphate as the curing cat- buffer such as sodium metaborate to the formu-
alyst leads to high levels of wrinkle resistance. An lation. This raises the pH of the final finished
excess of glyoxal appears to serve as a chelating fabric sufficiently to eliminate the need for an
agent and diluent for aluminum ions, thus mod- afterwash to remove acidic catalysts.
erating the tendency of the catalyst to degrade The glyoxal-glycol process has been conducted
the cellulose.19,20 at curing temperatures of 145–160°C on all-cotton
fabric. The catalyst was aluminum sulphate buff-
Glyoxal-Glycol Mild Cure Process ered with aluminum dihydroxyacetate stabilized
with boric acid (Fig. 6). Curing times of 15–20 s
The addition of polyhydric alcohols19 –21 to the were sufficient to impart a high level of DP prop-
treating formulations results in improved fabric erties when using 1,6-hexanediol as the crosslink
whiteness and increased durable press (DP) rat- modifier. The addition of small amounts of phos-
ings. ␣-Hydroxy acid was added as catalyst acti- phoric acid to the formulation was beneficial in
vator to suppress the strength losses in treated preventing deactivation of the catalyst by fabrics
cotton. This means the curing temperature for containing traces of alkali left from the scouring
crosslinking could be lowered to 115–125°C and operation. The effect of the buffer was to improve
the order of effectiveness of various acid catalysts the fabric strength retention and whiteness ob-
is as follows: succinic ⬍ lactic ⬍ malic ⬍ glycolic tained.22
⬍ citric ⬍ tartaric acid. A silanol-terminated sil-
icone fabric softener appeared to exert a synergis- Monomeric Adducts of Glyoxal with Ureas
tic effect with glyoxal and aluminum sulphate in
improving the DP ratings. The extent to which a The cyclic addition product of glyoxal with N,N⬘-
straight-chain glycol increased DP performance dimethylurea is the most important member of
depended primarily on the molecular chain length this family and is named as 1,3-dimethyl-4,5-di-
of the glycol. The optimum length was approxi- hydroxyethyleneurea (DHDMI).
mately six atoms, excluding the terminal hy- DHDMI imparts a moderate level of wrinkle
droxyl groups. The role of the glycol is as a resistance to cotton fabric in the presence of
crosslink modifier, which alters the spatial con- MgCl2, zinc nitrate, or zinc fluoborate as curing
figuration, polarity, and flexibility of the three- catalyst. Zinc fluoborate was by far the most ef-
dimensional crosslink network produced in the fective curing catalyst in terms of wrinkle recov-
cellulose. ery angles observed before and after multiple
launderings performed on the DHDMI finished
High-Temperature Glyoxal-Based Processes fabric. DHDMI was found to be less effective than
DMEU. However, it produced a finish very resis-
The advantage of high-temperature curing is that tant to chlorine damage even after multiple laun-
15 to 60 s of residence time of the fabric in the derings under severe conditions, and was supe-
curing oven is sufficient to achieve cellulose rior to DMEU in this respect. DHDMI produced a
crosslinking,21 and also to heat-set the polyester finish that offered greater resistance to acid hy-
to final fabric dimensions. Aluminum chlorohy- drolysis than that of DMEU, but inferior to that of
droxide Al2(OH)5Cl.2.5H2O is an effective high- N,N-dimethylolurea. Zinc salt catalyst with
temperature (170°C) catalyst in the presence of DHDMI gives first-order reaction whereas with
␣-hydroxy acid for all cotton fabrics. magnesium salt, it gives zero-order reaction. With
A mixture of aluminum sulphate and magne- zinc salts catalysis the reactivity of the ring hy-
sium sulphate has been recommended as a non- droxyl group is increased by the N-methyl sub-
yellowing catalyst for the application of glyoxal at stituents present in DHDMI. Overall, the SN1
temperatures such as 190 –205°C in the presence mechanism is followed by DHDMI with cellulose,
of a reactive silicone, which appears to exert a whereas the SN2 mechanism in the case of
synergistic effect with the glyoxal.22,23 At a high DMEU-treated cotton.
level of DP performance, equal to that imparted The stability of DHDMI at room temperature
by a conventional treatment with DMDHEU, the makes it suitable for use in finishes that are to be
glyoxal-finished fabric had higher tearing postcured some months after the fabric has been
strength and slightly lower breaking strength padded with the treating solutions and dried.
than the DMDMEU-treated fabric. This compar- The use of polymeric additives such as acrylate
ison was made on 65/35 polyester/cotton. A fur- copolymers or crosslinkable silicones in 10%
FINISHING OF TEXTILE MATERIALS 637
Tear
Wrinkle Strength Breaking
DP Recovery Retained Strength
Agent Catalyst Rating Angle (%) Retained (%)
by neighboring cellulose hydroxyls causes the tention of fabric whiteness, and free from odor
crosslinks to be mobile. (Table V).
The newer catalyst which is more effective than In the presence of weak bases as esterification
sodium carbonate or tertiary amines is alkali metal catalyst, the reactions proceed by intermediate
salts of phosphorous-containing minerals acids. The formation of cyclic anhydrides of BTCA as the
order of decreasing effectiveness is as follows: actual esterifying agents. The catalyst increases
NaH2PO2 ⬎ Na2HPO3 ⫽ NaH2PO3 ⬎ NaH2PO4 the rate of anhydride formation as well as the rate
⬎ Na2H2P2O7 ⬎ Na2P2O7 ⬎ Na3P3O10 ⫽ (NaPO3)6 of crosslinking. It was found that loss of weight
⬎ Na2HPO4 ⫽ Na3PO4 ⬎ Na2CO3. corresponded to water loss as anhydrides were
Sodium hypophosphite is, however, most ex- formed on heating BTCA and CPTA, cis-cyclopen-
pensive. Thus, other catalysts are used in the tane tetracarboxylic acid.33
mixture. The effect of highly polar additives on BTCA
A variety of polycarboxylic acids29 –32 have reaction with cellulose has been studied. Trieth-
been compared as DP finishing agents with so- anolamine acted as a crosslink modifier that en-
dium hypophosphite catalysts. Most of these acids hanced DP appearance rating, laundering dura-
imparted high DP performance initially, as evi-
bility of the finish, and fabric strength retention.
denced by DP ratings of 4.3– 4.7 and conditioned
N,N-Disubstituted amides increased the condi-
wrinkle recovery angles of 295–300°. However,
tioned and wet wrinkle recovery, as well as DP
the resulting finishes differed considerably in du-
rating, but had no effect on fabric strength reten-
rability to alkaline laundering. The acids ar-
tion. The amides may have altered the hydrogen
ranged in order of decreasing durability, together
with the maximum number of machine washings bonding, the degree of fiber swelling, and the
and tumble drying cycles withstood, were as fol- crystallinity of the cotton. Recently, malic acid31
lows: butane tetracarboxylic acid ⬎ mellitic ⫽ tri- activated by BTCA or small amounts of BTCA
carboxylic ⬎ thiodisuccinic ⬎ citric ⬎⬎⬎ maleic with high concentrations of citric acid as a DP
⬎ succinic acid. finishing agent have been found be very effective.
The tear strength retention was 60 – 68% with Finishing of silk fabrics with a mixture of
tri- or tetra-carboxylic acids compared with 99% glyoxal and urethane compounds has also been
respectively for the DHDMEU finish catalyzed by reported by Kawahara and Coworkers34 –36 for
MgCl2. This is attributed to the buffering action of improving the crease recovery, drape, and tear
sodium hypophosphite catalyst and the absence of strength. In addition, good durability against ul-
Lewis acid catalysts. traviolet rays and laundering has been demon-
Thus, 1,2,3,4-butanetetracarboxylic acid (BTCA) strated from glyoxal and urethane mixture finish-
is the most effective of the polycarboxylic acids ing agents.
studied with respect to the level of DP perfor- Tsang and Dhingra37 have also given a brief
mance, speed of curing, laundering durability, re- account of various finishes used for silk fabrics.
FINISHING OF TEXTILE MATERIALS 639
Silicon
Bath Composition (wt %) PE Softener Organo-Reactive Reactive
3% Rucolase ZEV, 1 : 10 liquor ratio, pH 4.5–5.5, 55°C, 30– Increase in softness, better handle and
45 min for knitted cellulose fabrics washing quality
Process designed by TS chemicals for woollen/worsted Improved handle, softness, pilling resistance,
fabrics cleaner surface, and improved drape
Treatment of cotton/wool blend fabric
3 or 5% owf cellulase, pH 4.5, 1 : 10 liquor ratio, 60°C, 1 Strength loss 12–18%, abration resistance
h (at 60°C, 4.5 pH) loss 40–55%, softness increased 50–55%,
pilling resistance improved, dry W.R.
improved 5–11°
3 or 5% owf protease enzyme pH 8.5 (NaOH) 1 : 10 liquor
ratio, 60°C 1 h (60°C, 8.5 pH)
Silk waste treatment
Soaping for 30 min (25% owf 1 : 30 liquor ratio Wetting time reduced, removal of impurities,
removal of kitties (only 2–3% remain after
the treatment)
Cellulase enzyme 30–40 per g of fabric, buffer of 5.2
pH, 50°C, 3 h
Degummase treatment: degummase 1000 L, 50°C, pH 8.7
(buffer), 3 h
Bleaching by H2O2
neutral cellulase, depending on the wash time. fabric of polynosic rayon fibers was napped using
But, the use of acid cellulases causes more back- emery paper, scoured, treated with an aqueous
staining than the neutral or alkaline stable cellu- solution of 6 g/L Enzylon® CM (cellulolytic en-
lase enzymes. The redeposition of indigo removed zyme) at 35°C to give a fabric with peach-skin-
from the fabric that remains suspended in the like surface without naps. Stone washing using
liquor is termed backstaining. It is undesirable endoglucanases (fungal cellulase) for reduced
because it decreases the color contrast of the backstaining on fabrics has also been disclosed.68
stone-washed samples.
The pH of the washing liquor exercises great Pretreatment Processes
influence on backstaining which is minimum at
Desizing of Cotton Fabrics
pH 7. Thus, neutral cellulase could be preferred
for denim washing. Typical recipes for denim Because of the selective action and ecofriendli-
washing are shown in Table IX. Some researchers ness, enzymes are commercially used for desizing
have also reported the combined effect of cellulase cotton, i.e., breaking down of starch into water-
and pumic stone washing or combined alpha- soluble forms by the amylase enzymes.69 –71 The
amylase with cellulase enzyme for single-step amylase enzyme is highly specific and reacts only
procedure. The production of a peach-skin-like with starch. Thus, cellulose remains intact and
surface of cellulosic or its blends has also been there is no strength loss. Amylase breaks starch
disclosed in a patent by Toyo Boseki.67 A woven into low molecular weight dextrin that could be
0.5–2.0 gpl cellulase acid enzyme, MLR 1 : 10, pH Weight and strength loss are a function of time,
4–5.5 (NaOH: acetic acid buffer) 55–60°C temperature, and amount of cellulase
Stone-eze威 (stoneless finish) Improved handle, less strength loss, less damage to surface
Acid cellulase, MLR 1 : 10, 4–5.5 pH (buffer), 55°C Acid cellulase does more backstaining (function of time),
reproducibility more, if enzyme concn is less and
stability to pH broad
FINISHING OF TEXTILE MATERIALS 645
washed off easily. Nowadays, liquid bacterial all the impurities but protease enzymes that are
preparations of higher activity are also available capable of hydrolyzing the peptide bonds are for
for use. silk degumming77,78 and in wool processing/fin-
The desizing process consists of the following ishing as well. Proteases have been reported to
steps: 1. impregnation of the enzyme solution into give the fabric a softer handle and reduced lous-
the fabric for thorough wetting of the fabric at 70°C iness. The procedure recommended for scouring
or higher with suitable nonionic wetting agents; 2. and bleaching of the spun silk is: soaping, treat-
incubation, where breakdown of starch into water- ment with enzyme degum of suitable concentra-
soluble dextrins takes place by steaming at 110 – tion at 50°C for 3 h, at pH 5.2, and bleaching with
115°C for 15–20 s; and 3. after wash to remove the hydrogen peroxide. Such a process enhances the
size breakdown products from the fabric. surface characteristics, wettability of the fabric,
and removes the impurities as well. Some of the
Removal of Cotton Pectin enzymes used in processing of natural fiber fab-
rics are listed in Tables X and XI.
Cotton pectin forms 1% and is a major component
of the impurities present in the primary wall of
fiber as well as deposits in the lumen from dried WATERPROOF BREATHABLE FABRICS
protoplasm. Pectins are present as water-insolu-
ble calcium, magnesium, or iron salt in cotton. Waterproof/moisture permeable fabrics from sev-
This insoluble form can be converted into soluble eral synthetic fibers have been designed for ski-
form by exchange of polyvalent cations with wear, track suits, rainwear, and mountaineering
monovalent cations such as ammonium or so- clothing.67 The application of a one-piece overall
dium. The conventional process of pectin removal made from a woven nylon fabric (30-den flat nylon
involves a severe boil with high concentration of warp yarns; weft of 900-den air jet textured
caustic soda for many hours, but with the pectin- yarns) in the 1986 dogsled race in Alaska has
ase process, the pectin could be removed effec- been described by Hunton.79 A nylon glove with a
tively in a short time. Chloroform-extracted cot- Gore-Tex威 liner was also designed for this pur-
ton is treated with suitable enzyme concentration pose.
at 50°C and pH 5. It is observed that enzyme Woods80 has studied the relation between
degradation is very rapid and after 1 h, 70 – 80% clothing thickness and cooling during motorcy-
of the pectin gets degraded. cling in the range from ⫺1 to ⫹24°C. To maintain
a normal body temperature in winter on a motor-
Pretreatment of Wool and Silk cycle without a protective shield, much thicker
clothing (a mean clothing thickness of 20 mm)
In the recent past, there has been an ever-in- inside the windproof oversuit is needed at 5°C,
creasing interest for the introduction of enzymes but it is only effective if perspiration does not
in wool processing.72–75 Areas of special interest accumulate inside the clothing.
are increased comfort, increased softness, surface Lightweight fabrics coated with poly(vinyl
appearance, and reduced pilling performance. chloride), polyurethane, and other synthetic rub-
The treatment of wool by Bactosol® SI has a bers have become increasingly popular for foul-
significant effect in reducing wool shrinkage and weather clothing. Although garments manufac-
at the same time improving the whiteness as com- tured from these fabrics provide exceptional pro-
pared with the untreated sample.75 In a patent,76 tection against rain and to a less extent, wind
antifelting property has been achieved by plasma penetration, condensation can accumulate on
treatment followed by treatment with a protease, their inner surface. This problem arises because
preferably subtilisin. of the water-vapor impermeability of the polymer
Application of enzymes in degumming of silk coating. A buildup of moisture vapor inside the
and bast fibers has also been reported. Recent clothing may therefore cause discomfort.
research has shown the effectiveness of enzy- To overcome this problem, breathable polymer
matic action on processing of waste-silk fabric. coatings are now available that have made possi-
Silk spun from waste silk poses some problems ble great improvements in the comfort of this type
during processing because it contains many im- of clothing. Microporous polytetrafluoroethylene
purities in the form of broken chrysallis, straw, (PTFE) Gore-Tex® laminates have been success-
lignin, hair, and some cellulosic particles. Con- fully introduced as breathable fabrics.81,82 Com-
ventional processes are not effective in removing parative assessment of Gor-Tex® and Neoprena®
646 BAJAJ
30
Cotton
Boerozym AC, CA3, CB# enzyme 1 : 30 MLR, Wt loss 6%, T.S. loss 5%, 10% after
pH 5 (citric acid: NaOH buffer), 40°C alkaline boil, Boerozym AC shows
high swelling, CA3 shows poorest
whiteness
Alkaline peroxide boil
31
Cellulase enzyme, 1 : 10 MLR, pH 5, 30 s, T.S. loss up to 40% (for 24-h treatment),
stored at 60°C in a moist cabinet average DP reduces, whiteness
reduces 8–10%, capillary action rise
increases, Tegewa drop spread
increases
21
Pectinase process to remove pectin, fabric wt 70–80% pectin removal after 1 h
80 g, 3 g/mL of enzyme concn in 1 L, pH
5, 60°C
32
Silk
Silk degumming Biopril 50 (2.5 g/L), 1.0 g/L Up to 90% degumming achieved
nonionic wetting agent, pH 9, 50°C for 6
min
vapor barriers in firefighter suits has also been increased three-fold. The manufacturers claim
made.83 that these PTFE membranes contain approxi-
A breathable fabric is waterproof and breath- mately 9 billion pores per square inch, with a pore
able because of the enormous difference between volume of up to 80% and a maximum pore size of
the size of a water droplet and a water-vapor 0.2 m.
molecule. The former is 100 m in diameter
whereas the latter is 0.0004 m, i.e., there is a Solvent Exchange
factor of around 250,000 between the two sizes.84
In this process, a polymer dissolved in a water-
miscible solvent is coated thinly onto the fabric.
Classification of Breathable Fabrics The porous structure is developed by passing
The breathable fabrics can be classified into three through a coagulation bath where water displaces
main categories85,86: 1. coated fabrics87–90; 2. lam- the solvent. For example, the textile substrate is
inated; and 3. high-density woven fabrics. coated with polyurethane solution where dimeth-
ylformamide is being used exclusively as the sol-
vent and the fabric is passed through a coagula-
Microporous Coating and Laminating Films tion bath containing water, where water displaces
The microporous barrier layer “breathes” primar- the solvent to give a porous structure.
ily through a permanent air-permeable pore
structure. Diverse techniques have been used to Phase Separation
manufacture microporous coatings and films. The
The coating polymer is applied from a mixture of
most important methods are listed below.
a relatively volatile solvent with a proportion of
higher boiling nonsolvent. Precipitation of the
Mechanical Fibrillation
polymer as a microporous layer occurs as the true
For certain polymers, biaxial stretching produces solvent evaporates faster during the subsequent
microscopic tears throughout the membrane, drying process. For example, Ucecoat 2000, a
which imparts a suitable microporous structure. polyurethane-based coating, operates on this
For example, PTFE membranes are used in the principle. Here a lower boiling solvent (methyl
Gore-Tex®, two-layer and three-layer laminates. ethyl ketone) evaporates preferentially as the fab-
The thin microporous membrane is made from ric passes through the oven thereby increasing
solid PTFE sheet by a novel drawing and anneal- the concentration of the nonsolvent in the coating.
ing process. In drawn form, the tensile strength is When the concentration of the nonsolvent reaches
FINISHING OF TEXTILE MATERIALS 647
subsequently extracted from the dried film or reversible hydrogen bonds with water-vapor mol-
coating with water to get a microporous structure. ecules. These groups thus act as “links or con-
duits,” allowing water-vapor molecules to pass
Electron Bombardment through the polymer from an area of high concen-
tration to an area of low concentration. This
A process has been developed for rendering the mechanism is specific for water vapor and does
solid coated fabrics microporous by bombarding not allow oxygen, nitrogen, and CO2 molecules,
the polymer coating with an electron beam. The which are incapable of forming hydrogen bonds.
technique involves feeding the coated fabric be- The water-vapor transmission (WVT) rate in
tween two electrodes generating high-voltage hydrophilic polymers under steady state is given
electrons which can be focused into discreet by the relationship,
beams with a drill through the coating without
damaging the fabric beneath. DS共P1 ⫺ P2 兲
WVT ⫽
t
Ultraviolet–Electron Beam Curing
where P 1 ⫺ P 2 ⫽ partial pressure gradient be-
The Sunbeam process is used to manufacture mi-
tween the two surfaces; t ⫽ thickness of the poly-
croporous films and coatings in situ by crosslink-
mer coat; D ⫽ diffusion constant governed by the
ing suitable monomers with electron beam or ul-
nature of the hydrophilic polymer; and S ⫽ solu-
traviolet light. Radiation curing has the following
bility coefficient. The solubility coefficient de-
advantages over the conventional methods: 1. low
pends largely on the molecular attraction be-
energy consumption; 2. low environmental pollu-
tween the polymer chains and the penetrant. For
tion; 3. fast curing, and thus fast processing; and
example, hydrophilic polymers have high solubil-
4. short start-up times.
ity coefficients.
Sympatex membrane (made of copolyester) has
Crushed Foam Coating no pores thus making it absolutely tight to water
Mechanically foamed and thickened lattices are and wind. However, this can allow water vapors
coated onto fabric and dried. Large surface pores to pass through by the use of a special type of
are formed which are compacted by calendering polyester whose molecules have water-vapor
through a pressure nip to yield a microporous transporting properties.
fabric. Tarka fabrics are also given a water-repellent
finish using 3M’s Scotchgard™ fabric protector.
Penn-Nyla showed that “unlike other transfer
Hydrophilic Coated and Laminated Fabrics coatings which leave a relatively impervious poly-
Hydrophilic coated and laminated fabrics trans- urethane film on the fabric, the Tarka process
mit water vapor selectively by a molecular pro- incorporates a microporous layer, allowing a
cess, i.e., by absorption, diffusion, and desorption greater degree of breathability.”
through the solid polymer layer. Such a polymer The Tarka fabrics have been extensively tested
film or coating shows no evidence of voids or mi- for practical performance in relation to water-
croporous structure, and thus is not susceptible to proofness, breathability, and durability by the
surface contamination by dirt, dust, etc. Ken Ledward Equipment Testing Service, a well-
The sensitivity of solid polymer to liquid water known sportswear testing company, in a program
is extremely variable and depends on their phys- giving the equivalent of 8 months of rigorous use
ical and chemical composition. The solid polymer on demanding environments such as the UK’s
may be completely soluble in water, for example Lakeland Fells and the Austrian Tyrol. The Brit-
poly(vinyl alcohol), polyacrylic acid, etc. They are ish Textile Technology Group has also performed
too sensitive to liquid water and would either tests based on both existing and proposed new
dissolve completely or else would not withstand standards for coated fabrics and for waterproof
the vigors of normal use. Thus, they are unsuit- breathables. Penn-Nyla reports that Tarka fab-
able for use as permanent, flexible fabric coatings rics passed all these tests by at least twice the
or polymer films. required levels.
The efficiency of water-vapor diffusion through
intermolecular pores can be increased by creating New Route
a succession of chemical groups (i.e., amines, hy- A very novel approach to achieve a waterproof
droxyl, carboxyl) which are capable of forming and breathable fabric, using nonporous mem-
FINISHING OF TEXTILE MATERIALS 649
branes, has been developed by the Shirley Insti- ● Burlington’s Versatech威 microfiber-based fabric
tute in Manchester (now part of the British Tex- ● Hoechst with its microfiber Trevira-Finesse威
tile Technology Group). They developed a hydro- (0.65 dpf) polyester, used by Rotofil AG to
philic polymer, which is now made by the weave their CLIMAGUARD威
Baxenden Chemical Company named Witcoflex ● Formesa Taffela Co. Microfeel威 with nylon
Staycool威. Baxenden has perfected the techniques and polyester microfibers
for coating this novel polymer onto fabrics where
● Asahi Kasei developed Leofeel威 and Super
it forms a nonporous layer. In the same way as
microft威 with microfibers
the Sympatex威 film, this hydrophilic coating
breathes by passing water-vapor molecules along ● Toray Ind. with Dyna-bright威 to weave their
“built-in stepping stones” to the outside of the H2Off威
fabric. Being nonporous, it also prevents liquid ● Kuraray with WRAMP to weave Arcus威
water from entering. The properties of the final
coated fabric depend on a number of factors but Combination
Baxenden says that when the coating is applied
correctly it should have the following perfor- Breathable fabrics can also be obtained by the
mance specifications: 2500 – 8000 g/m2 water-va- combination of the above-mentioned techniques,
por transfer per day on nylon and 3500 –10,000 such as a hydrophilic finish on a microporous
g/m2 per day on polycotton and textured fabric. structure to upgrade the water resistance of the
The hydrostatic head which the fabric will sup- microporous coatings. For example, Ucecoat®
port should be a minimum of 150 cm. NPU 2307 finish on top of Ucecoat 2000 (S) mi-
Witcoflex Staycool can be applied by standard croporous coating is used.
direct or transfer coating machines. A new devel-
opment from Baxenden is the X-Liner, a water-
Mechanism of Water-Vapor Transmission
proof breathable drop liner which is sewn be-
tween the outer fabric and the lining. In this case, Through textiles, water vapors and liquids are
moisture-vapor permeability of over 12,000 g/m2 transmitted by the following mechanisms: 1. sim-
per day can be achieved. ple diffusion through the interyarn spaces. The
resistance to diffusion is governed by the fabric
construction, i.e., the size and concentration of
Uncoated High-Density Fabrics the pores and the fabric thickness; 2. capillary
transfer through fiber bundle. The liquid water is
In open-weave fabrics, water vapors transmit wicked up through the yarns and desorbed or
mainly through interyarn spaces and transfer evaporated at the outer surface. The nature of
through individual fibers, and fiber bundles are these interfiber spaces is determined by the
relatively unimportant. Thus, fabrics of similar choice of yarn and fabric construction; and 3. dif-
open construction, weight, and thickness are ex- fusion through individual fibres. The ability of the
pected to show similar transmission rates, irre- fiber to undergo water-vapor diffusion depends on
spective of the type of yarn or fibers used. As the the hydrophilic or hydrophobic nature of the fiber.
size of the interyarn spaces decreases, the second- A polymer coating consists of a mesh of rela-
ary transmission mechanisms become more im- tively thin sections, representing the areas of
portant. Thus, tightly woven fabrics constructed polymer covering the yarn crowns and thicker
from absorptive or hydrophilic fibers are more sections where it has penetrated into the fabric
transmissive of water vapor than similar con- interstices.
struction of nonabsorptive, hydrophobic fibers. In the case of hydrophobic fabrics, the trans-
A number of high-density fabrics have been mission occurs mainly through the interstices of
marketed recently. They use yarns produced from nonabsorptive, hydrophobic fabrics, and hence
microfibers of less than 1 decitex per filament. through the predominately thicker areas of the
Example of some microfiber yarns used for high- polymer barrier whereas cotton or polyester/cot-
density fabrics are: ton substrates can also utilize the hydrophilic
properties of the fiber bundles under the thinner
● ICI with Tactel威 micro/24 carat (0.4 dpf) areas of the polymer coating and thus tend to be
polyamide used, by Finlayson in Microspirit威 more water-vapor permeable than coated hydro-
● DuPont de Nemours fibre: Supplex威 (0.9 dpf) philic of similar structure. Table XII shows the
polyamide water-vapor resistance of clothing.
650 BAJAJ
Table XII Water-Vapor Resistance of Clothing medical purposes; (b) protection of the textile it-
Fabrics for Comparison self from biodeterioration caused by mold, mil-
dew, and rot-producing fungi; and (c) protection
Water-Vapor Resistance for textiles from insects and other pests. A repre-
Fabrics (mm Still Air)
sentative range of bacteria and microorganisms91
PVC coated 1000–2000
used in the evaluation of the antimicrobial activ-
Waxed cotton 1000⫹ ity of protective textiles are listed in Table XIII.
Leather 7–8 Of these, Staphylococcus aureus, a pathogenic
Typical nonwovens 1–3 Gram-positive bacterium, is the most frequently
Woven microfiber (nylon or evaluated species, for it is the major cause of
polyester) 3–5 cross-infection in hospitals as well as in commer-
Closely woven cotton 2–4 cial and home laundry practices.
Ventile 128 3–5 In an extended review, Vigo92 has covered var-
Two-layer PTFE laminates 2–3 ious aspects of finishes, their types, modes of ap-
Three-layer laminates plication, and efficacies against different microor-
(PTFE, PE) 3–6
ganisms and insects, and specific requirements
Microporous PU (various
types) 3–14
related to end-use, such as persistence and resis-
Open pores 3–5 tance to biological attack as a function of fiber
Sealed pore 6–14 type, as well as synergistic, antagonistic, and cu-
Hydrophilic PU coated 4–16 mulative effects of such finishes on other textile
Witcoflex staycool in properties and many other aspects concerning fi-
nylon, polyester 9–16 ber/finish interactions.
On cotton, poly/cotton 5–10
Gram-positive bacteria
Staphylococcus aureus Pyrogenic infections Hygienic, medical
Staphylococcus epidermidis Body odor Aesthetic
Corynebacterium diptheroides Body odor Aesthetic
Fungi
Candida albicans Diaper rash Hygienic
Epidermophyton floccosum Infection of skin and nails Hygienic
Trichophyton interdigitale Athlete’s foot Hygienic
Trichophyton rubrum Chronic infections of nails and skin Hygienic
Viruses
Poliomyelitis virus Poliomyelitis Medical
Vaccinia virus Localized disease induced by vaccination Medical
against smallpox
Protozoa
Trichomonas vaginalis Trichomoniasis vaginitis Hygienic, medical
Trematode (blood flukes) Schistosomiasis Hygienic, medical
Schistosoma japonicum
FINISHING OF TEXTILE MATERIALS 651
SILK-LIKE POLYESTER
Topical Finishes
The enhancement of polyester properties by treat-
ment with aqueous sodium hydroxide was recog-
nized soon after the invention of polyester.99
Figure 16 Shrinkage mechanism: parallel and serial
Treatment of untextured yarn fabric with alkali
yarn structures. produces softer tactility with a less synthetic
hand. A calendar heat-set and caustic soda sapon-
ified fabric was patented a few years later as the
mixture, just like Quiana (nylon yarn produced by treatment was said to produce high fabric lustre
DuPont) and the other is a serial kind. without paper-like handle.
The parallel structure is made by mixing fibers Polyester undergoes nucleophilic substitution
of different shrinkage levels either by using dif- and is hydrolyzed by aqueous sodium hydroxide.
ferent polymer fibers or by mixing fibers of poly- The hydroxyl ions attack the electron-deficient
ester drawn at different temperatures. The serial
type is produced by random heat setting along
individual fibers during fiber processing.97 The
fibers shrink randomly with the heat treatment.
In the parallel structure, higher shrinkage com-
ponents form a core, and lower shrinkage compo-
nents form waves or loops around the core. How-
ever, in the serial type structure, higher and
lower shrinkage parts are distributed randomly
in the yarn and there is no core. The resulting
fabric from serial type arrangement of different
shrinkage level fibers showed a more natural silk
look than the parallel type (Fig. 16).
Uchida98 has also demonstrated the role of
shrinkage in producing Shingosen. Fukuhara
from Toray Industries has shown that, for the
production of Shingosen, initially the dry-heat
shrink process was tried and later the wet-heat Figure 17 Shrinkage diagram of polyester fabric af-
shrink process. But, a double-shrunk fabric ap- ter caustic treatment.
FINISHING OF TEXTILE MATERIALS 655
Sample A Sample B
it dropped slowly to 90 V (Table XV). The reduc- polyester fiber fabric is remarkably softened by
tion in static charge accumulation of the alkali- relaxation. The improved fabric handle results
treated polyester may be attributed to the surface from desizing, shrinking of fibers, and relaxing of
saponification of polyester as indicated by the in- internal residual stress. Subsequent weight re-
creased number of hydrophilic [COOH] and OH duction caused by alkali treatment produces an
end groups, wicking, and, to a limited extent, the “effective gap” between the starting fibers or
moisture regain. yarns and the resultant fibers. The minimum
The effect of the caustic solution on a polyester amount of weight reduction necessary to split fi-
fabric depends also on the fiber type, fabric con- bers is expected to be approximately 10%. By
struction, and heat-setting conditions. Bright fi- using discriminant analysis with the primary
bers with a round cross-section lose weight more hand values as variables, a distinctive zone for
slowly than delustred fibers with a multilobal silk-like and peach-skin-type polyester fabric can
cross-section. Reasons for this difference in the be found.
rate of weight loss could be attributed to the fol- Sodium hydroxide treatment reduces electro-
lowing: static charge generation from 280 to 100 V and
the half-life from 5 to 2.5 s. Solbrig and Oben-
● For a given linear density, a multilobal fiber dorf101 have reported the considerable weight loss
would have a larger surface area than a after saponifying polyester fiber containing 2%
round fiber. TiO2 (Fig. 19) and the pitting on the surface,
● The presence of delustrant may accelerate observed through scanning electron microscopy,
the weight loss of the fiber. mainly axially oriented along the fiber surface.
● For a peach-like effect, high-solubility poly- Treating polyester fiber with 10% aqueous NaOH
mers or inorganic particles are incorporated at 100°C (by steaming) for 45 min produced hy-
in PET melt, which essentially solubilize or groscopic polyester fiber.
leach out to give a pit effect on the surface,
thereby affecting the feel and handle of the
fabric. This radical alteration in the surface
has been ensued by the Japanese to prepare
dry touch yarn. Microcraters result in low
convex– concave configuration.
● Samples appear to lose weight faster after
texturing. For example, the losses in weight
of nontextured yarn and textured yarn when
treated with 5% caustic soda at 104°C for 1 h
were 35 and 41%, respectively.
So, the emerging technologies that will domi- 30. Welch, C. M. Text Chem Color 1997, 29(2), 21.
nate the research-and-development strategies of 31. Welch, C. M.; Peters, J. G. Text Chem Color 1997,
chemical manufacturers and textile finishers into 29(10), 33.
the next decade are: ecofriendly formaldehyde- 32. Welch, C. M.; Peters, J. G. Text Chem Color 1997,
free finishes; bioprocessing of textiles; silicones 29(3), 22.
33. Yang, C. Q. 211th American Chemical Society
softeners; waterproof breathable fabrics; and
National Meeting Cellulose, Paper and Textile Di-
plasma treatment.
vision, New Orleans, Mar. 24, 1996; Yang, C. Q.
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