Indi an Journal of Fibre & Textile Research

Vol. 26. March-June 2001 , pp. 162- 186

Ecofriendly finishes for textiles

P Baj aj"
Department of Tex tile Technology, Indian In stitute of Technology . New Delhi 110 0 16. Ind ia

The challenges facing the tex tile fi nishing industry have intensifi ed durin g the last decade. Cu rrent awareness of the
negati ve enviro nmental impac t of chemi cal processing of tex tiles, combined with increased strict legislati on on industri al
efnu ents, has led to the search for advanced , non-poll uting processes for treatin g natural and manu fac tured fib re fabri cs. In
thi s paper, an overview of ecofri endl y fi nishing treatments. which inc lude formalde hyde- free fi ni shes, enzy matic softening.
use of sil icones, low-temperature pl asma and antimicrobial lantibac teri al fini shes, has been give n. Appli cati on of breath able
coatings has also been demonstra ted.

Keywords: An ti bacteri al fini shing . Enzy matic softening. Glyoxal, Moisture vapour permeable coatings. Plasma trealment,
Polycarboxylic acids, Silicones

1 Introduction Cross linking occUlTed within th e access ibl e regions

Today, with the increas in g awareness of
environme ntal concern s, an important leg islati on o n
eco-tox icological considerati ons has been introduced .
It is related to such important issues as health and
safety during storage, applicati on and use, and safe
di sposal o f che mi cals into landfill and water or
release in air during che mica l processing of textil es.
These have imposed changes in che mical fini shes and
fini shing methods. So, integrated po lluti on contro l is
necessary for developing eco fri e ndly processes in thi s
new millennium. Th e driving force in th e rece nt
technol ogy has been the eco no my a nd ecol ogy, and
fi ni shers are therefore trying to produce te xtiles more
effi ciently, with less wate r and less polluti on 1-4 .
In thi s paper, a comprehe nsive rev iew o f the
vario us fini shing treatme nts leading to wrinkl e- free
fab rics with good a nd soft handle through
form aldehyde- free finishes, bio-fini shing a nd
breathable coatings is given. Developme nts in pl as ma
treatment and antibacteri al/antimi crobi al fini shes ha ve
also been hi ghli ghted.
2 Easy Care Finishes
2.1 Cotton
In the 1980s, the market fo r easy care and durabl e
press fi ni shes was do minated by N,N'- 1,3-dime thylo l-
4,5-dihydroxyethy lene urea (DMDHEU ), usin g
magnesium chloride as the ac id catalyst to initi ate
chemi cal cross linking of cellulose c hain mo lec ul es.
"Phone: 659 1403; Fax: 009 1-011 -6526 154;
Emai l: pbajaj @lex lile.i ild.ern el.in
(i.e. the a morphous regi ons o f the fibre) prov id in g an
increase in th e fibre res istance to deformati on and
improved elasti c recovery from defo rmation .
One approach to limit th e probl e ms of
formaldehyde release has been to use glyoxalurea-
based deri vatives such as 1,3-d imethyl-4,5,dihydrox y-
ethy lene urea 5 (DHDMJ). Thi s is a zero form aldehyde
based cross li nking agent for cotton th at reacts th rough
the ring hydro xy l groups in th e 4,5-pos iti ons of
cellulose. Howe ver. such deri vatives are more
ex pensive and somewhat less e ffec ti ve th an
DMDHEU at the sa me add -on level, poss ibl y du e to
hydantoin formation , and he nce more acti ve curing
system s are ofte n required .
DHDMJ imparts a moderate level of wrin kle
resistance to cotton fabric in presence o f MgC h , zinc
ni trate or zinc fluroborate as curin g ca talyst (T abl e I).
Zinc flu roborate was by far the most effect ive curing
ca talyst in terms of wrinkl e recovery angles observed
before and after multiple launderings carri ed out on
th e DHDMI fini shed fabri c. Zinc salt catalyst w ith
DHDMI gi ves first order reacti on whereas with
magnes ium sait, it g ives zero order reacti on. With
zinc salts catalys is, the reacti vity o f the ring hydroxy l
group is increased by the N-me th y l subsitu ents
present in DHDML
The stability o f DHDMI at roo m te mperature
makes it suitabl e fo r use in fini shes that are to be
postcured so me month s after th e fa bri c has been
padded with the treatin g so luti o ns and dri ed . T he use
o f polymeri c additi ves such as acry late copo lymers or
cross link abl e sili cones in 10% DHDM I formul ati o ns
 BAJAJ : ECOFRIENDLY FINISHES FOR TEXTILES 163

Table I - Comparison of some formald ehyde-free DP fini shin g agents with DMDHEU
Age nt Catal ys t DP rating Wrinkle Tear strength Breaking strength
recovery angle retained retained
deg % %

DHDMI Zn(BF4 h 3.4 254-27 1 43-51 59-73

Zn (N0 3h 3.2-3.3 249-265 64 82
MgC lz 2.8-3.3 227-247 62-66 .go
MgCl z-CA 2.5-3.0 241-244 45

BTCA NaHzPO z 4.0-4.7 285-300 51-67 49-59

NazHPO J 4.0-4.2 286 63-66 59-72
NaHzP04 3.5-4.4 282-304 51-59 50-55
Na zHP0 4 4.0 267-285 65-73 55-76

CA NaH zPO z 3.3-4.0 240-268 62 50-61

Mi xed 3.8-4.0 247-264 55-64

DMDHEU MgClz 4.3-4.8 261-280 49-57 44-60

DHDMI-1.3-dimeth yl-4.5-dihydroxyethylene urea; BTCA- 1.2,3A-butane tetracarboxy lic ac id: and

CA- citric acid.

produce a marked increase in DP performance. The 7 C.llulos.-OH + 0 = CH-CH= 0

moi sture regain and affinity for CI Direct Red 81 Prr dry
_ C.llulos.- 0-.......... ......-O-C.llulo
shown by DHDMI-cross linked cotton was same as for CH-CH
HO""""'- "-OH
untreated cotton. But the affinity of the cotton for
(1 )
direct dyes is greatly decreased when cotton cellulose
is crosslinked with conventional N-methylol agents 6 . (1) + HOCH CH 0H ~ Cellulo.e -0-..........
2 2
/ O- C.II
AI 2IS0,)) CH-CH
An alternative approach has been based upon the 0/ ----""""'0
use of glyoxal or polycarboxylic acids:
"'" CH 2- /'
CH 2

2.1.1 Glyoxal
9 Fig . 1 - Reacti on of glyoxal/glycol with cellulose (ref. 7)
Glyoxal 7- in presence of an acid catalyst, such as
boric acid, ammonium chloride and aluminium
sulph ate, on heating g ives monoacetals and diacetal s
of glyoxa l with cellulose (Fig. I). Free aldehyde
groups present due to the single-ended attachment of
glyoxal as in I in Fi g. I were found to be re movable
by oxi dati on with chlorous acid or reduction with
potassium borohydrid e. Since glyoxal mol ecule can
form four link ages to cellulose, glyoxal may be
regarded as tetrafunctional. Magnesium chloride was
used as a catalyst in early studies for applying a very
hi gh g lyoxal concentration (10% by wt.). In th e
absence of active hydroge n compounds as co- reactive
additives ,the fabric we ight gai n was onl y 1.4% . With
active hydrogen compounds (a lcoh o ls , phenols,
amides or thiol s) as co-reactant, much higher fabric
weight ga in could be obtain ed . But probl e m with
MgCI 2 is that it prod uces fabric yellowing an d severe
fabric stre ngth loss. Th e use of aluminium sulphate as
the curing catalyst leads to the hi gh levels of wrinkle
resi stance. Excess of g lyoxa l appears to serve as a
1111
chelating agent and diluent for aluminium ions, thus
moderating the tendency of the catalyst to degrade the
cellulose.
2.1.2 Mild Cure Process
The addition of poly hydric alcohols in the pad bath
results in low cure process with improved fabric
whiteness and increased DP ratings. Alpha-hydrox y
acid was added as catalyst activator to suppress the
strength losses in treated cotton . This mea ns th e
curing temperature for crosslinking could be lowered
to lIS-125 C. The order of effecti veness of vari ous
acid catalysts is as follows:
Succinic < lactic < malic < glycolic < citric < taJtaric acid .
The extent to which a straight-chain g lycol
increased DP performance depended primarily on th e
molecular chain le ngth of the g lycol. The optimum
le ngth was approximately six atoms, exc luding the
terminal hydroxyl groups. The role of the glycol is as
a crosslink modifi er(product II in Fig. I) which alters
164 INDIAN.I . FIBRE TEXT. RES. , MARCH-J UNE 200 1

th e polarity and tlexibility of the three-dimensional Table 2-Colllpari so n o f et hylene g lycol (EG) and diethy lene
cross link network in cellulose. Performance of glyco l (DEG) as co-reactants for g lyoxa l in DP fini shin g of cotton
ethylene glyco l (EG) and diethylene glycol (DEG) at 125C (ref. 7)

wi th respect to DP rati ng is show n in Table 2. "Pad bath cOIll~os iti o n : 4.8 % g l ~oxal Wt. DP
EG conc. DEG conc. Mo le rati o add-o n rating
2.1.3 High-temperature Curing Processes % % g lyco ls/glyoxal %
The adv antage of hi gh-temperature curing is th at 0 0 2.9 3.0
15-60 s residence time of the fabric in th e curin g oven 2.6 0 0.5: 1 4.6 3.5
5.2 0 1:1 7.5 4.2
is sufficient to ac hieve cellulose cross linking, and also
10.3 0 2: 1 7.4 3.9
to heat-set the polyester to final fabric dimensions in 20.6 0 4:1 7.2 4.0
polyester/cotton blends. Aluminium chlorohydroxide 41.3 0 8: I 7.9 3.8
[Ab(OH hC J.2H 20] appears to be effective as hi gh 0 8.8 1: 1 13 .8 4.5
0 17.7 2:1 17 .0 4.5
temperature (170C) catalyst in presence of ex-hydroxy 5.2 4.4 1:0.5: 1 10.1 4.1
acid . 5.2 8.8 1:1: 1 13.2 4.4
A mi xture of aluminium sulph ate and magnesium 5.2 13.3 I: 1. 5: I 15.6 4.4
5.2 17.7 1:2: 1 16. 1 4.5
sulph ate has also been recommended as a non-
ye llowing catalyst for the appli cation of glyoxal at "4.8 % g lyoxa l + ei th er or both g lyco ls, 0.77 % A I2(SO.).\. 16H]O +
0.37 % tart aric acid + reactive silicone so ftener ( I % so lids) and
temperatures such as 190-205 C in th e presence of water.
reactive silicones. A sil anol-terminated silico ne
softener appeared to exert a synergisti c effect with
res ilience. It is believed that hydro lyzed starch may
glyoxal and aluminium sulph ate in improv ing the DP
modi fy the cross linking reactions and the structure of
ratings . At a high level of DP performance, eq ual to
the crosslinks, th ereby improve fabric resili ence.
that imparted by a conventional treatmen t with
DMD HEU, the glyoxal-fini shed fabric had hi gher 2.1.4 Inorganic Phosphates as Crosslinking Agents
tearing strength and slightl y lower breaking strength The phosphory lat ion of cotton cellulose can be
than the DMDH EU- treated 65:35 polyester/cotton carried out by heat curin g of fabric impregnated either
fabric. A further process improvemen t co nsists in with a I: I mixture of mono- and di-sodium phosphate
add ing a buffer such as sod ium metaborate to the or preferably sod ium hexameta phosp hate. When the
form ulati on. This rai ses th e pH of th e final finished phosphorus co ntent of treated fabric exceeds 1.6%,
fab ri c sufficientl y to eliminate the need for an the fibres are found to be insoluble In
afterwash to remove aci di c catalysts. cupri eth ylenediamine hydrox ide so lution, and the
In another stud/, glyoxa l-glyco l finis h has been cellulose appears to be crosslinked.
used at curing temperatures of 145- 160C on all- 2 Cell-OH + NaH 2 P0 4 ---7 Cell O-P(O) (ONa)- O-Cell
cotton fabrics . The catalyst was aluminium sulphate
buffered with aluminium dih ydroxyacetate stabilized Crosslinking of cellulosic fabric can also be
with boric acid. Curing peri ods of 15-20 s were ac hi eved by phosphorylation with a mixture of urea
sufficient to impart a hi gh level of DP properti es and mono- or di-ammonium phosphate. A moderate
while using 1,6-hexa nediol as the crosslink modifier. level of DP along with flame retardant properties is
The addition of small amounts of phosphoric acid to imparted usi ng pad-dry-cure method at a sufficiently
the formulation was beneficia l in preventing hi gh degree of phosphorylati on. High levels
deactivation of the catalyst by fab rics containing (approx .1 2%) of mon osod ium or monoammoniulll
traces of alkali left from the scourin g operati on. The phosphate and, in so me instances, very hi gh levels
effect of th e buffer was to improve the fabric strength ( 12-24%) of urea are required.
retention and whiteness obtai ned . 2.1.5 Durable Press (DP) Finishing with Pol yca rboxylic
Rafai e f a/. lo have reported th e treatment of cotton Acids " '6
fab ric with glyoxal/starch or hyd rolyzed starches/ Citric ac id was found to be rhe IllOS t effecti ve
MgCI 2.6H 20 catalyst/water system. Starch and polycarboxy lic ac id, in the absence of added catalyst
hydro lyzed starches are used along with glyoxal with by pad-dry-cure treatment, although it produced Illore
the possibility of th eir contribution in fa bric fab ric discoloration than the other agents. The cross links
 BAJAJ: ECOFRIENDL Y FINISHES FOR TEXTILES 165

were formed In cellulose by acid-catalyzed esterify ing agents l6 . Catalyst increases the rate of
esterification with citric acid itself, furnishing the anhydride formation as well as the rate of
protons needed for the autocatalysis. crosslinking. It was found that loss of weight
Polycarboxylic acids with 4-6 carboxyl groups per corresponds to water loss as anhydrides were formed
molecule in the presence of alkaline catalysts were on heating BTCA and cis-cyclopentane tetracarboxylic
found to be more effective than with acids having acid (CPT A).
only two or three carboxyl groups. Sodium carbonate Performance of various polycarboxylic acids has
or trimethy l amine was added as a catalyst. These also been compared with conventional methylol
salts act as buffers and greatly diminished acid- derivatives as DP finishing agents with sodium
induced tendering during high temperature curing. hypophosphite catalysts. Most of these acids imparted
The wrinkle-resistant finished fabrics obtained were high DP performance initially, as evidenced by DP
recurable. In the presence of heat, the ratings of 4.3-4.7 and conditioned wrinkle recovery
transesterification of ester crosslinks by neighbouring angles of 285-300 (Table I). However, the resulting
cellulose hydroxy Is causes the crosslinks to be finishes differed considerably in durability to alkaline
mobile. laundering. The acids arranged in order of decreasing
The newer catalysts which are more effective than durability, together with the maximum number of
sodium carbonate or tertiary amines are alkali metal machine wash ings and tumble drying cycles
salts of phosphorus containing minerals acids. The withstood, were as follows:
order of decreasi ng effectiveness is as follows: Butane tetracarboxylic acid> Mellitic =Tricarboxylic
NaH 2P0 2> Na2HP03=NaH 2 P0 3> NaH 2P04 > Thiodisuccinic > Citric > Maleic> Succinic acid.
> NaH 2 P20 7> Na2P20 7> Na3P30JO =(NaP0 3)6 The tear strength retention was 60-68% with tri- or
> Na2HP04 = Na3P04> Na2C03. tetra-carboxylic acids compared to 54% for
Sodium hypophosphite is, however, most DMDHEU finished fabric. This is attributed to the
expensive. Thus, other catalysts are used in the buffering action of sodium hypophosphite catalyst
mixture. and the absence of Lewis acid catalysts. Thus,BTCA
Welch and Peters 14 have reported the use of sodium
bromide as a co-catalyst for DP finishing of cotton o o
I II I II
fabrics with polycarboxylic acids which permits a HC - C - OH - H0 HC - C
decrease of as much as 75 % in the amount of sodium I _--=2=--~~ I "0
hypophosphite required as a curing catalyst. This HC - C - OH HC - C ........
I II I II
lowers the chemical costs and the amount of o o
phosphorus compounds that need to be recovered Polycarboxylic acid Cyclic anhydride
from spent treating solutions which, in many states,
cannot be disposed of in rivers or lakes. Tertiary o
I II
alkanolamines and their phosphoric and HC- C "
metaphosphoric acid salts also help in decreasing the I ........ 0 + HO - R cellulose ~
amount of hypophosphite catalyst needed l4 . HC- C
I II Cellulose
A feature of triethanolamine as a crosslink modifier o
is that it increases the strength and flex abrasion Cyclic anhydride
resistance retained by the fabric during DP treatment. o
I II
In this respect, triethanolamine is superior to glycerol
H? - C - 0 - R Celiulose
or pentaerythritol. The sodium salts of alpha-hydroxy
polycarboxylic acids can serve as direct replacements HC - C - 0- H
I II
for sodium hypophosphite or other phosphorus o
compounds as curing agents for 1,2,3,4-butane
tetracarboxylic acid (BTCA). Polycarboxylic acid
bonded to cellulose
In presence of weak bases as esterification catalyst,
through an ester linkage
the reactions proceed by intermediate formation of
cyclic anhydrides of BTCA (Fig. 2) as the actual Fig. 2 - Reacti on of po lycarboxylic acid with cellulose (rcf. 16)
166 INDIAN J. FIBRE TEXT. RES .. MARCH-JUNE 200 1
is found to be the most effective of the polycarboxylic
acids studied with respect to the level of DP
performance, speed of curing, laundering durability,
retenti on of fabric wh iteness and free from odour.
Recently , malic acid activated by BTCA or small
amounts of BTCA with hi gh concentrations of citric
ac id as a DP finishing agent have also been found to
be very effecti ve.
Saraf 17 has reported th e use of two commercial
non-formaldehyde crosslinking agents, Natrium- NFO
and Natrium-CRA , for cotton and polyester/cotton
blends. At 15 % Natrium-CRA bath concentration, the
wrinkl e recovery angle of cotton was found to be
240C when cured at 170C for 1 min.
2.1.6 Usc of Functional Polymers
Efforts have been made to add chemically modifi ed
starch products to the crosslinking formulation in
order to minimize the great loss in the tensil e strength
of the finished fab ri cs. In this context, poly(ac rylo-
nitrile)-starGh graft copolymers based on hyd ro lyzed
and ox idized starch es were syn th es ized 1s . 19 . The effect
on fab ri c performance was fo und with DMDHEU .
Crease recovery angles and tensile strength of th e
cotton fabric fini shed in th e presence of polyacrylo-
nitrile-starch graft copolymer based on hydroly zed
and oxid ized starches increase by increasing th e
concentration of the grafted starch. However, dry
crease recovery angle of cotton fabrics fini shed in the
presence of grafted starc h products was low.
2.2 Finishing of Jute with Glycols and Acrylic Acid
Jute fabric has been modified by using ethyl ene
glyco l (EG), diethylene glyco l (DEG), polyethyl ene
glyco l (PEG-400 and PEG 1500) and poly vin yl
alcohol (PV A) in th e prese nce of Ab(SO-lh as the
catalys t by pad-dry-cure techn ique 20 . Treatments of
oxy-jute (copper number 12.6) with 8% DEG in th e
prese nce of 5% Ab(S04h as the catalyst follow ed by
drying at 95 C for 5 min and curing at 125C for 5
min produced fabric s with 2600 (W+F) wrinkle
recovery , 3.2 cm bendin g length and imp roved
flexibi lity . While 8% PEG 1500 produced fabri cs
with 238 WRA and improved effects in ten ac ity and
elonga ti on-at-break and hence in resi li ence.
Ghosh & Das2 1 also reported the mod ificat ion of
jute fabrics using acry li c acid (A A) as a fini shin g
agent in the presence of K2S20 S and Na}P04 catalysts
separately or in suitable combinations, employ ing
pad-dry-cure techniqu e. Treatment with 10% acrylic
ac id at 30C and pH 7 produced optimum effects; a
batching time of 45-60 min at 30C followed by
drying of th e batched fabric at 95C for 5 min and
cu ring of the dried fabric at 140C for 5 min produced
jute fabrics with 238 (W+F) wrinkl e recovery and 2.6
cm bending length while untreated jute fabri c had
143 (W+F) wrink le recovery and 3.8 cm bending
length. Na3P04 catalyst allowed es terificati on of AA
wi th cellulosic, hemicellulos ic and li gnin constituents
of jute, and K2S20 S catalyst faci litated radical
polymerization of acrylic acid, leading to some degree
of crosslinking of the po lymer chain of jute.
2.3 Finishing of Silk Fabrics 22J2
Finishing of silk fabrics with a mi xture of glyoxal
and ureth ane compounds has bee n reported by
-..1 f
K aw ahara ef a 1.212 or'Improvlllg
. tIle crease recovery ,
drape and tear strength . In addition , good durability
against ultrav iolet rays and laundering has been
demonstrated from glyoxal and urethane mixture
finishing agent.Tsang and Dhingra 2-1 have also given a
brief account of various finishes used for silk
fabrics.A non-form aldehyde crease-resistant fini sh for
si lk has been developed by using citric acid as a
crosslinking agent 25 . The finished silk had a dry
wrinkle recovery ang le of more th an 280 compared
to 265 for th e untreated control. The fin ished fabr ic
retained 84 -98.5 % of its breaking strength and th ere
was an increase of 40-80% in its tear strength . The
whiteness retentio n was about 65 %.
Durable press fini shing wi th BTCA prod uced
excellent res ults26 . Both the dry and wet resiliency of
fini shed silk were remarkably improved. The fini shed
fabric had a dry wrinkle recovery angle (WRA ) of
301-311 and wet WRA of 252-263 compared to
265 and 217 res pectively fo r the untreated control.
After 50 cyc les of home laundering, almost all th e
fi nished fabrics retained a DP ratin g higher th an 3.5
compared to 1.9 for the co ntrol which was washed
once. The dyeing behaviour of crease-resistant sil k
finished with BTCA and citric ac id has also been
studied using acid, direct and cationic dyes 27 . Whether
dyed befo re or after finishi ng, th e fabric had good
dyeabiliry with improved resili ence.
A new easy-care fini shing method 28 for silk fabrics
with epoxy resin EPTA has been introduced . Silk
 BAJAJ: ECOFRIENDL Y FINISHES FOR TEXTILES
fabric was padded twice with 100giL EPTA aqueous
solution, dried at 40C and then treated with 8 giL
a2C03 at 75 C for IS min . The wet crease recovery
angle was improved from 200 (untreated) to 282
after finishing. The breaking strength of finished silk
increased by more than 10% and the whiteness
decreased by about 2 .8%. Finished silk fabrics have
good laundering durability; after 20 cycles of home
laundering,the wet resiliency retained was 95 % of that
of the unwashed fabrics durability.
Shiozaki and Tanaka 29 have analyzed the reactivity
of epoxide onto silk and demonstrated that the
modifications with epoxide onto silk improve
moisture absorption, chemical resistance, and wash
and wear properties . The four epoxides used were
glycidol, ethylene glycol diglycidyl ether, tolyl
glycidyl ether and resorcinol diglycidyl ether. From
the amino acid analysis of the silk treated with
epoxides, it may be concluded that the epoxides react
with the side chains of the silk fibroin , such as lysine,
hi stidine, arginine and tyrosine, thereby suggesting
that most of the weight gain due to the fibre treatment
is distributed uniformly throughout the cross-section
and does not occur near the fibre surface. They also
reported that epoxides form crosslinks between the
adjacent silk fibroin molecules and the hydrogen
bonds between the hydroxyl groups of epoxide
molecules attached to the side chains of the silk
fibroin 'o.
Chemical mod ification of silk fibres by graft
copolymerization of vinyl monomers and by reaction
of epoxides and dibasic acid anhydrides, for example
phthalic, succinic and glutaric anhydride, have also
b een reporte d .31..11-. Th e gra f
t col "
po ymenzatlon .
reaction
of vinyl monomers onto silk fibres may be achieved
by various meth ods, such as radiation , chemical- or
photo-induced initiation. The use of chemical redox
sys tems in aqueous media has played a major role for
both sc ientific and technological purposes. The study
of photo-initiatio n systems has begun recently. Their
primary advantage is that some properties of the
grafted polymer are imparted to the fibrous substrate
without seriously affecting its basic structure and
morphology.
3 Role of Softeners in Wrinkle-free Garments 2,33-37
Durable press fabrics suffer decreased tensi Ie
stre ngth , tear strength and abrasi o n resistance, and
often have a stiff, harsh and uncomfortable feel. A
quality fabric softener/lubricant will readily mitigate
167
these deficiencies , adding value to a wrinkle - free
garment. One function of a softener is to modify the
hand or feel of a fabric to reach the desired effect. The
softener must also lubricate the fibres to increase
abrasion resistance and tear strength. The softener
also functions as a sewing lubricant, as high needle
speeds can generate enough heat to melt and fu se
synthetic fibres. Sewing damage, such as broken or
fused yarns, causes garments to be rejected by the
customer.
There are four basic classes of softeners, viz.
anionic, cationic, non-ionic and blended systems. The
general characteristics of these softeners are discussed
below in greater detail.
3.1 Anionic Softeners
The anionic softeners are generally sulphated or
sulphonated compounds used primarily to lubricate
yarns or fibres through processing. Generally, the
anionic softeners are good lubricants, provide soft
handle and show good stability to alkaline conditions.
Most of them show good heat stability and some have
good yellowing resistance.
However, anionics tend to provide inferior softness
compared to the cationics and non-ionics.
Furthermore, they have limited durability to
I
laundering or dry cleaning. The major limitation
comes from their negative charge, which causes
incompatibility in resin finishing baths and makes
them most sensitive to water hardness and
electrol ytes.
3.2 Cationic Softeners
The cationic softeners are nitrogen contall1l11g
compounds which include fatty amino amides,
imidazolines, amino polysiloxanes and quaternaries.
This class of softeners provides a very soft, silky hand
and improves the antistatic properties of a fabric .
They tend to improve strength properties, such as tear
and abrasion, and the sewability of a textile ,
especially when a polyethylene softener is present in
the system.
Cationic polyethylene softeners are effective in
processing napped or raised pile fabrics where fibre-
to-metal friction (f.!F/M) reduction is essential. In
napping softeners, the cationic materials such as fatty
amino amides and imidazolines are typically blended
with an efficient polyethylene lubricant. Palmitic and
stearic acid based saturated fatty groups are preferred
to reduce yellowing and to avoid rancidity, which
168 INDIAN J. FIBRE TEXT. RES., MARCH-JUNE 2001

may occur with oleic or tallow fatty acid types. To
achieve maximum lubricity and strength properties,
many formulations are made with a significant portion
being polyethylene. Typically, a blend will contain 2
parts polyethylene lubricant to I part aminoamide or
imidazoline. Cationic softeners, as a result of their
positive charge, will be attracted to a cotton or
synthetic fabric and can be readily exhausted from a
long bath or a dyebath. They tend to be compatible
with most resin finishes. However, the cationic
softeners have a tendency to change the shade or
affect the fastness of certain dyestuffs. The
development of a fishy odour on a fabric can be
another problem with certain systems.
3.3 Non-ionic Softeners
Non-ionics are the most widely used softeners
which include polyethylenes, glycerides such as
glycerol monostearate, ethoxylates such as
ethoxylated castor wax, coconut oil, corn oil, and
ethoxylated fatty alcohols and acids. The non-ionic
softeners offer excellent compatibility in resin baths
and are easy to mix into a formulation. They generally
have little or no effect on the shade of dyed fabrics.
Most are resistant to discoloration and yellowing.
textile applications are generally in the range of
10,000-12,500 centistoke. Polydimethylsiloxanes
impart desirable properties to fabrics due to their
flexible polymer backbone, stable bonds and low
intermolecular forces. However, the softening effect
is not very durable to washing since there are no
reactive sites in the polydimethylsiloxane polymer.
3.4.2 Reactive Silicones
These are polydimethylsiloxane polymers modified
with silane hydrogen or silanol functional groups.
Two mixed polyorganosiloxanes are also made, e.g.
poly(methyl hydrogen siloxane). Conventional
reactive silicones form a crosslinked siloxane network
on the fabric surface in the presence of water and an
organometallic catalyst. The crosslinked polymers
provide durable softeners better than POMS. Silanol
functional polymers are also the basis for silicone
elastomers and textile finishes to improve hand and
performance of durable press fabrics .
3.4.3 Organo-functional Silicones
Aminofunctional groups which are bound to
polydimethylsiloxane backbone improve the orientation

3.4 Silicone Softeners 3lI- 48

Silicones have been used as textile softeners since
1960. Initially, polydimethylsiloxane (POMS) was
used. But in the late 1970s, the introduction of (OSi silicone L-45)
aminofunctional polydimethylsiloxanes opened new

cHrrjoJ~!f0- r
dimensions for textile softening. They confer high
lubricity to the fibres owing to their low surface
energy. Methyl groups are the most important of the
organic substituents used in commercial si licones, the
vast majority of which are polydimethylsiloxanes
(POMS). Silicones have some unique properties
I I
o-17- CH3
CH3 CH3 R CH3 x

(Magnasoft Plus)
I
I
NH2
1 Y
I

including thermal/oxidative stability, low-temperature

flow ability, low viscosity change with respect to
temperature, high compressibility, low surface tension
(spreadability), hydrophobicity, dielectric properties
and low fire hazard.
Silicone softeners currently available can be
classified into the following three groups (Fig. 3):
Non-reactive silicone softeners
Conventional reactive softeners
Organo-functional silicone softeners.

3.4.1 Non-reactive Silicone Softeners

Non-reactive silicone softeners are based on
Fig. 3- Chemical structures of reactive and non-reactive sili cone
polydimethylsiloxanes. The viscosities useful for softeners (ref. 41)
 BAJAJ: ECOFRIENDLY FINISHES FOR TEXTILES
and substantivity of the sili con on the fibre . The
improved ori entation of aminofunctional silicones
leads to an extremely soft hand, which is frequ entl y
described as 'Supersoft ' . In thi s, organo-reactive
groups such as amines, epox ides and alcohols are
introduced in the PDMS .
New Amino FUllctiollal Silicones: Amino gro up
(primary to terti ary) in polydimethylsiloxanes was
substituted. The structure of the amino group In
PDMS is as und er:
Amino Abbreviation R
Primary -NH2
Secondary NH-methyl -NH-Me
NH-butyl -NH-(CH2hMe
NH-Iauryl -NH-(C H2)I IMe
NH-cyclohexyl -NH-C 6 HII
Terti ary -NEt2
On com paring the effects due to pnmary,
secondary and tertiary am ines, it is ev ident that
wh iteness, water absorbency and soi l release improve
with the increasing degree of substitution from
primary to secondary to tertiary.
Improved whiteness arises from the chemical
structure of the am ino functional groups. The th ermal
yellowing is du e to oxidati ve decomposition of the
am ino group, form ing chromophoric groups. The
degree of imp rovement in whiteness on changing
from primary to tertiary amino groups parallels the
slowing of thermal degradation, as the number of
alkyl substituents increases. Only the si licones
substituted with secondary ami nes show values as
good as the si licones based on the amino ethyl and
am inopropyl groups which have been commonly used
so far. An optimal combi nation of treatment effects
can be obtained with secondary am inofunctional
silicones. All silicones substi tuted wi th secondary
ami nes, except for the NH-butyl si licone, produce a
soft hand th at is simi lar to that produced by the usual
NH-ethylene ami ne modified silicone. NH-ethylene
amine substituted si licones have a relatively strong
water repellent effect. This effect is lower for
si licones substituted with secondary amines .
Di fferences in soil release properties are minimal
between th e si licones with secondary amine
substi tuents.
Czech et 01.41 demonstrated the effect of
"Magnasoft TA-\5" add iti ve (which is based on
dialkyl oxalate) on ye ll owing properties of amino
169
modified silicone softeners. This chemical modificati on
res ults in the formation of a stable emulsion of amide
modified silicone with non-yellowing attributes and a
distinguishable change in softening properties. In
addition, aminosilicone emulsion modified with T A-
15 exhibits film forming and elastomeric properti es .
A new product Magnasoft SRS , which is a blend of
Magnasoft Plus (amino-silicone) and polydimethyl-
siloxane-amino polyalkylene oxide block copolymer,
provides good softness along with soil release on
polyester/cotton blends . Magnasoft HSSD with both
pendant alkyl amine and polyether based polydi-
methylsiloxane terpolymer has been evaluated as a
softener for soi l release on wri nkle-free garments in
conjunction with fluorocarbon soi l release agents.
Softeners for terry towels available in the market
are classified on the basis of their durability as
permanent hydrophilic and semi-durable hydrophli c.
Permanent hydrophilic: These softeners are usuall y
organo-modified silicones. These products offer an
excellent handle along with hydrophili ci ty, which can
last for the lifetime of the fabric (15-20 washes).
Semi-durable hydrophilic: Softeners classified
under this category are normall y a combination of
silicone and cationic components. Towels finish ed
with such softeners sometimes specify that it will
show improved hydrophilicity after one wash. These
softeners offer an adequ ate-to-excellent hand le and
low hydrophi licity.
Resi l Chemicals42 have introduced a range of
si licone products, for example RESIL Hydra range is
a new generation of softeners catering to the special
requirements of a terry towel finish -excellent
hydrophilicity, soft fluffy handle, durability and non-
yellowing-leaving the towels look fresh wash after
wash.
Silicones have also been used to improve the all-
rou nd properties of si lk fabrics 43 . Table 3 shows the
results of the crease recovery properti es of si licone
fin ished fabrics . It is observed that the recovery angle
is hi gh in amino silicone compared to fatty amide,
polysiloxanes and si licone softeners. The improved
recovery angle is because amino silicones are
crosslinked with the fibre. The recovery properti es of
the silicone finished fabrics after washing does not
show any marked diffe rence in the recovery angle.
Shenai 44 used non-ionic surfactants with
considerable water solubility made from the mixed
type of poly(orga no-s iloxanes). A very useful
170 INDI AN J. FIBRE T EXT. RES., MARCH -JUNE 200 1

Table 3 - Effect of silico ne fini shes on silk fabrics 4.1

Cellulase Enzymes
CrYltoll ine Amorphou s
Chemicals Crease recovery ang le Bendin g le ngth reoion s ~ ,-- regi ons
deg em ~~~~=~;:~~~~=~~~~~~~
I
Warp We ft Warp We ft (a) Endo-b- 91ucana u tGs)

Untrea ted 79 66 2.0 1.45

--->. ~ t 1-.1
Fatty amides silicones (b ) CQllobiohydr olo u (CBHs )
_/ t _ /"
3% 83 94 1.91 1.30 .... '" ~:::-r=
4% 86 96 2.0 1.32
(e)
5% 89 99 2. 1 1.34
Amino silicones
b- Gluco s rda u
3% 91 100 1.64 1.20 (d )
.. - Glucon
4% 93 105 1.74 1.29
5% 95 108 1.76 1.27
Fig. 4 - Schematic representation of synergi sti c acti on of
Am ino-e poxy silico nes e nzy mes o n cellulose (ref. SO )
3% 91 104 1.70 1.1 7 highly resistant to biodegradation by micro-organisms,
4% 95 108 1.75 1.22 but they undergo very effective degradation via natural
5% 97 113 1.79 1.25
chemical processing and POMS breaks down into
Reactive polysilaxane lower molecular weight silanol s. No adverse effects
2% 92 100 1.95 1.25 were seen for seed germination. Their molecul ar size
3% 93 104 1.98 1.27 prevents th em from pass ing through th e bi ological
4% 95 107 2.05 1.29 me mbranes of fish or other animals. POMS fluids
Po lysi loxa ne exhibit insig nificant biological oxygen de mand
1% 89 10 1 1.71 1.20 (BOD). Thus, the new aminofunctional silicone
2% 91 ]03 1.73 1.26 softeners46 -48 have many advantages over initial
3% 94 109 1.75 1.31 POMS like low yellowness, high softness, require low
Softener based on concentration and e nvironme ntally safe. In additi o n,
mi cro-e mul sion they have the ability to blend with other organic
3% 87 97 1.66 1.20
soften ers while retaining thei r ori gi nal performance.
4% 87 98 1.74 1.22
4 Biotinishing49. 61
Organic fun cti onal silicone
elastomer
Processing of cellulosic fabrics and garme nts with
cellu lase enzymes, generally referred as biofinishing,
4% 92 101 1.80 1.26
started in the late 1980s. Superior hand and novelty
5% 98 109 1.84 1.27
finish es on rayo n, line n and cotton knits can be
property of such non-ionic conde nsates is that unlike achi eved with cellulases.
other s ilicones, which require an e mul s ifying agent Cellulases are mUlti-compone nt e nzyme syste ms
prior to their application to textil e mate ri als in the commonly produced by soi l-dwell ing fun gi and
for m of an e mul sion , they are so luble in wate r, --and bacteria. The most important organi sms are
T richoderma, Pe nicillium and Fusarium. Cellul ases
he nce do not require an emulsifying agent.
co nsist of at least three enzy me sys te ms working
3.4.4 Environmental Consideration for Silicone-based sy nerg isti cally togeth er as illu strated in FigA.
Softeners454l! Endoglucanases or e ndocellulases hydro lyse ce llul ose
In the environment, the re is no ev idence that random ly along the c hai ns, preferenti all y the
si licones adversely affect eco-systems no r has there amorphou s region. Cellobiohydrolases or exo-
been a ny ex perience o f toxic o r mutagenic effects on cellul ose attac k the chain ends and prod uce primari ly
animals or aquatic life. POMS is ecolog ically inert cellobiose coupl ed w ith the binding domains
and has been found to hav e no effect on aerobic or associated with the e nzyme. Th e cellob iose and an y
anaerobic bacteri a. It does not inhibit th e biological sma ll c hain o li go mers produced by exo-cellul ases are
process by which waste water is treated . Silicones are then hydro lysed by the third enzy me B-4-glucosidase
a minor part of the waste water di scharged . They are into g lucose.
 BAJAJ: ECOFRI ENDLY FINISH ES FOR T EXTILES
En zymes are acti ve at atmosph eric press ure in the
te mperature ra nge o f 30-60C. Based on th eir
sensiti vity to pH , they are cl ass ifi ed as :
Acid stabl e (pH 4. 5-5 .5)
Neutral (pH 6 .6-7 )
Alkali stabl e (pH 9-10)
Biofinishin g cons ists o f a ce llulase enzyme
treatment to g ive a partial hydro lys is of cotton fibre,
with a weight loss o f around 3-5 % and stre ngth loss
54
o f 2-7 %. However, Kumar et al. have reported the
strength loss (25-30 %) of cotton knit a nd viscose
rayon for hi gh surface po li shing under ac idi c
conditi ons at 60C. With pro pe r co ntro l of pH and
te mperature, standard who le acid cellul ases can be
used to fini sh del icate ce llul os ic fabri cs (Fig . 5).
The effect of ex isting dyes and the cross linkin g
agent on the reactiv ity o f ce llul ase has been studi ed in
depth . It see ms th at the pl a nar stru cture o f vat dyes
with larger molecul ar sizes th an indi go dye pl ays an
important rol e in inhibiting the acti on o f cellulase.
Cotton/wool bl ends (90 : 10 and 70: 30) have al so been
treated with both cellul ase and protease e nzy mes at
two different concentrati ons fo r improv in g th e surface
properti es.
Enzy matic so ftenin g of co tto n and co tto n bl e nd
fa brics res ults in :
less fuzz and pilling,
better fabri c fee l,
increased gloss or lustre, a nd
increased durab le softn ess.
In the case of knitted goods , thi s treatme nt is hi ghl y
reco mme nded because of tens io n-free process ing
co nditi ons alo ng w ith ag itati o n co upl ed w ith abras ion
of the garment to obtain th e mos t e ffec ti ve e nzy mati c
treat ment.
The cffec t of e nzymati c treatmc nt on woo ll e n
fab ri cs has also been studi ed by Pant a nd Tay al55 .
Bending le ngth of woo l decreased whe n th e
co ncentrat ion of e nzy mes was inc reascd. Protoso l
caused co mparative ly more decrease in st iffn ess th an
the other two enzy mes. T hu s, the fabric beca me soft
and suppl e after treatme nt w ith enzymes. C rease
recovery ang le of fab ri c inc reased o n in creas ing the
concen tratio n of e nzymes. Max imum im prove ment in
crease recovery was fo und w he n fa bri c was treated
with tryps in and degum mase e nzy mes whe reas
17 1
;! 30 ~~~~~h~~~~Cf Mod u ole su rfacct poli shi ng -
ACCf pl ob l. b ul k
High su rfa ce
po lishing-Lp w
2
.. Acceptab le
b u lk
bulk
o Cotto n kni t
.c
0, 18 rza Visc os e rayon
~
;; 12
u
.0
~ 6
50 55 60
Pr ocess temp Clr ature.oC
Fig. 5 - Effect of e nzy me treatm ent temperature on fabri c
strength loss (ref. 54)
protosol caused co mparativ ely less increase in crease
recove ry . Thus, th e c rease recovery property of wool
fa bric improved when th e fabri c was treated with
enzy mes . As the co nce ntrati on o f protosol was
in creased, great loss in tearing strength of woo l fabri c
was observed . Wh en the fabri c was treated with
degummase, there was so me loss in strength but it
was not as severe as in case of protosol- treated
sa mpl e. Trypsin also reduced the stre ngth of wool
fabri c, but it was sli ghtl y more as compared to that in
case o f degummase.
6
In anoth er stud/ , cotton and woo l fabri cs were
treated with low- tempe rature oxygen pl as ma or
e nzymes or both for studying their mechanical and
dyein g properties. Pl as ma pre treatme nt of wool
caused an increase in stre ngth and a hi ghe r rate of
weight loss in the subseque nt protease treatment.
Whe n th e wool was dyed with a levellin g acid dye,
th e equilibrium dye uptake did not change w ith
plasma or protease pretreatme nt , but the dyeing rate
increased w ith the plasma pretreatme nt. However,
w ith a milling acid dye, both increased greatl y in the
fo ll ow ing order :
Untreated < protease treatme nt < pl as ma treatment <
plas ma/protease treatme nt.
From these results, it was ass umed that pl as ma
attacks the surface o f the fibre whil e the e nzyme
affects mainl y the inne r part o f the fibres.
Shrink-res istance prope rties o f woo l treated with
serin e pro te inase Bactoso l SI have al so been
57
inves ti gated . Th e indepe ndent vari abl es we re the
conce ntrati o n of Bactoso l SI a nd the pH of th e
treatm ent bath . Th e pe rcentage area shrinkage, deg ree
o f wh iteness, loss of weight, and ball-pe ne trati on-
res ista nce loss were th e res ponses. The res ults showed
th at the enzy me co nce ntrati on a nd the pH valu e of the
treatme nt bath had a large influe nce on redu cing the
woo l shrin kage and on th e degree of white ness. T he
treatm e nt time also had a marked influe nce, mai nl y on
the mechani ca l pro perti es of th e knitted woo l fab ric.
172 INDIAN J. FIBRE TEXT. RES., MARCH-JUNE 200 1
Enzymatic hydrolysis to improve wetti ng and
absorbency of polyester fabrics has also been reported
by Hsieh and Cram 58 . Six hydrolyzing enzymes
(Table 4) to improve th e hydrophilicity of several
polyester fabrics were used. Five of the six lipases
improve the water wetting and absorbent properties of
reg ular polyester fabrics more than the alkaline
hydrolysis under optimal conditions (3N NaOH at
55 C for 2 h). Compared to aqueous hydrolysis, the
enzyme reacti ons are highly effective under more
moderate conditions, including a relatively low
concentration (0.0 I giL), a shorter reaction time (10
min ), ambient temperature of 25 C and no buffer.
Improved water wettabi lity is accompanied by full
strength retention compared to the significantly
reduccd strength and mass due to alkaline hydrolysis.
Interestingly, the wetting and absorbent properties of
sulphonated polyester and microdenier polyester
fab rics are also improved by lipase.
U Finishing of Lyocell 5%1
A concern encountered with use of Iyocell fibre s
has been th e fibrillation of fibre surfaces under
mechanical stress or when swollen with water. They
have a tendency to fibrillate because of th e hi gh
orientation and lack of lateral cohes ion. If con troll ed,
this fibrillation can provide a soft finish for Iyocell
fabrics, but under continued laundering the fibrillation
wil l become worse and may adversely affect th e
appearance and hand of a textiIe material. Fibre
processing parameters can, therefore, be adapted to
minimize the fibrillation problem in the spun fibres.
Fibre-reactive dyes, crosslinking resins and enzymc
treatments have been investigated as methods for
reducing the degree of fibrillation in Iyocell fabrics.
In one of the process, the fabric samples were
enzy me treated with a commercial whole cellul ase in
a Launder-O-meter machine at 50C for 60 min , both
with and without steel balls for agitation. The liquor-
to- fabric ratio was 20: 1 and an acetate buffer was
used to maintain the pH at 4.8 . A buffer control with
no enzyme was run in addition to three enzyme
Table 4 - Varieties of lipases used in improv ing th e wettabilily of polyesler fibres
Lipase Supplier or manufaclU rer Source
A ICN Hog pancreas
13 ICN Porc ine pancreas
C Sigma Wheat ge rm
0 Sigma Candida mgosa
E Genencor Inlenwli on<J1 Pselldol/IO/ws lIIe//{/ocii/(/
F Novo Nordi sk Aspergilllls ory~ae
concentrations (1.05, 5.3 1 and 16.04 %). Enzyme-
treated fabrics showed minimal fibril lation compared
to th ose submitted to simulated laundering condition s
without enzymes. Neither enzyme concentration nor
agitation affected the low-stress mechanical properti es
but did influence the tensile properties. The 10weSl
enzyme concentration was less detrimental to the
tensile properties, whil e inhibiting fibri llati on.
Production trials and monitoring in garment
process ll1g fac iliti es have show n that fabric
breakdown is significantly reduced when engi neered
component cel lulases are used as compared to
conventional who le cellulases. This is particularl y
evident on delicate fabric s and lyocell blends. Process
conditions used were : liquor ratio of 10: 1, pH 5.0,
treatment temperature of 58C and treatment time of
45-60 min. Th e enzyme dosages were adjusted to
achieve a hi gh degree of defibrill ation . On 100%
Iyocell, the handle attributes of the engineered
component cellulases treatments were assessed high er
than that of the whole cellulase, but the differences
were smal l at the dosages tested. Much clearer
differences were seen in the lyocell/cotton and
Iyoce ll/linen blends 60 . The panelists consistently rated
treatments by engineered component cellulases as
softer and bulkier compared to the whole cellulase,
irrespective of the dosages. This suggests that hand
preference may be directly related to the composition
of the enzymes and not to the enzyme dosage. These
three enzyme compositions influenced th e fabric hand
properties differently due to the possible differences
in their mode of action 61 .
5 Plasma Treatment62-~
The application of the plasma treatment has been
demonstrated for the surface modification of various
textiles. A lot of envi ronmental and production
problems can be solved by using a non-equilibrium
low-temperature plasma. The pl as ma processes are
dry ones and do not require wate r or non-aqueous
soluti on. Promising applications of gas discharge
plasma for the activat ion of chemical reactions in
liquids have also been reported .
58
Form ACl ivity Purily
Powder 30.8 units/mg 2.8% mo isture. 0.9% fat
Powder 16 ul1its/mg Diastase- free 12'K protein
Powder 7.6 units/Illg 95 % protein
Powder 250,000 units/mg 95 % protcin
Liquid 250.000 units >90%
Liquid 100,000 units >90%
 BAJAJ: ECOFRIENDL Y FINISH ES FOR TEXTILES
The plasma techniqu e is based o n ionised gases
produced by electri cal di scharges. In fact, the
coupling of electromagnetic power into a process gas
generates the plasma medium comprising a dynamic
mi xture of ions, electron s, ne utron s, protons, free
radicals and metastabl e exci ted spec ies which enable
a variety of surface processes, e.g. surface activation
for creati ng reactive etching, dissociation of surface
contam inants (scouring/bl eachin g) and deposition of
coatings for specific applicati ons. In all , the p lasma
treatment is a hi ghly surface speci fic of th e material
1000 A) which does not affec t th e bulk properties.
The mean depth of plasma acti ve species action in
63
po lymers is g iven in Table 5.
Depending on the gas pressure, two s ignificantly
different forms of discharges are known :
Corolla Discharge:
generated at gas pressures equal to atmosp heric
pressure
electromag netic field at > 15 kY
frequency range of 20-40 kHz
Glow Discharge:
generated at gas pressure in the 0 . 1-10 MPa range
electro mag netic field in the 0.4-8 .0 kY range
broad frequency range of 0 - 2.45 G Hz.
Strictly speak ing, both forms sho uld be regarded as
a source of low-te mperature plasma. In industrial
app li cations, a steady-state glow discharge capabl e of
operatin g at one atmosphere would all ow many
plasma-related surface mod ifi cat ion processes to be
done on the production line, rathe r than in ex pensive
vacuum syste ms that force batch processi ng.
Different gases can be used to achieve spec ifi c
chemical mod ificat io ns to the textile surfaces.
Properties en hanced include wettability, adhesion,
Tahle 5- Mean depth of plasma acti ve spec ies act ion in
pOlymers6.1
Active spec ies of co ld Energy. eV Mean depth of
plasma active spec ies
act ion
Atoms. radica ls. kT '" 0.01-0.1; E '" 0.5 > 0. 1 11m
excited molecu les
Ions. electrons 1- 100 Up to 10
mono layers
UV-photon s 5-20 Up to 10 11m
kT =Translat ional energy ; and E =Internal energy of partic le
173
cross linking, biocompatibility, protection and anti-
64 67
wear, and chemical affinity or inertness - . Relative
free-radical intensity of th e plasma-treated fibre s,
measured by ESR , increases in the following orde r:
Cotton> Wool> Silk> Nyl on 6 == PET.
The natural fibres, espec iall y cotton and linen,
showed larger free-radical intensity th an the
regenerated cellu lose and synthetic fibres .
The ill-situ plasma polymeri zati on for grafting of
polymers on to the textile surface has also received
co nsiderable attention for improving wettability.
Chemical grafting with various mo nomers onto
plasma-activated surface of cellulosics and other
fibres has been reported for accomp li shing specific
properties.
5.1 Shrinkproofing of WOOI68-7~
Th e most important factor for the renewed interest
in plasma techno logy came in 1987 from the new
legislation in Germany restrictin g the concentration of
AOX compounds in the discharged effl uents to 0.5
mg/L. The glow di scharge treatment of wool in non-
polymerizing gases like air, oxygen and nitrogen
provides hydrophilli ci ty o f the fibre surface and has
an excell ent shrinkproofing effect in co mbin ation
with ecofriendly res in. The new zero- AOX
shrinkproofin g treat me nt co nsists of ox idative step
and subseque nt application of a new resin based on
co llagen protei ns 68 which are cross linked with the
fibre surface by means of trifuncti onal epoxide
Araldit PT 8 10 and glycidyl acry late. Almost
complete shrink resistance of wool fabr ic and top is
acco mplished using the co llage n/ Araldit resin with
pl as ma pre-treated material (Fig. 6).
W akida et al. 69 , Kan et al.7o .72 and Rakowski 71 have
also made in-depth studi es on th e shrinkproofing,
dyeing and printin g of plasma-treated woo l. Wool and
poly(ethylene terephthalate) fab ri cs and film were
treated with low- te mpe rature pl as mas of helium/argon
or acetone/argon 69 under atmospheric pressure (Fig. 7)
for 10-180 s. Although argon itself cannot independently
generate a pl as ma under atmospheric pressure by
appl y ing hi gh frequency voltage, it is eas il y generated
by addi ng a s mall quantity of helium o r aceto ne to
argon gas. W ettability values of woo l and PET fabric s
treated with th e plasmas under atmos ph eri c pressure
are show n in Tab le 6. The helium/argon plasma
treatment was much more e ffecti ve in increasing the
174 INDIAN J. FIBRE TEXT. RES .. MARCH-JUNE 200 1

U: Untreated reference

P: Plasma - treated

C: .Caroat . treated fabric

'"
Q.
E
CAC: Carnal-treated fabric
after application of the @
'"
(/)
.S!
araldil-collagen resin

.0 PAC : Plasma-treated fabric

'"
u. after application of the
araldit-collagen resin
QJ)

o 10 t5 20 25
Falling shrinkage , %

Fi g. 6 - Anti -felting effect of Araldit/collagen res in on plasma

modifi ed fabrics compared with the Caroate pretreated material
(rcf. 68)

Table 6 --Effects of low-Iemperature plasma treallnent under

atmospheric pressure on water penetratio n of PET and wool
fabric s69
Treatment Time o f wa ter
penetration
s
PET
Untrealed >3600
Acetone/argo n plasma
lOs 11 67
285 Fig. 7 - Equipment for low- temperature pl as ma treatment un der
30 s
173 atmospheric pressure [( I ) power suppl y, (2 ) gl ass bell jar. (3)
60 s
24 brass electrode. (4) cock, (5) polyimide die lectric layer. (6)
180 s
specimen for treatment. (7,8&9) gas inlets, ( 10) acetone. and ( II )
gas outlet] (ref. 69)
Helium/argo n plasma
10 s 240
30 s 94 became wet very quickly. It is, therefore, assumed
60 s 60 that the surface structures of wool treated with both
Os 20
plasmas are so mewhat different. Probably, the
heliu m/argon plasma etches the fibre surface, whereas
Wool
Unlrealed >3600 the acetone/argon plasma causes polymerization of
Acetonc/argon pl asma aceto ne and produces hydrophi lic po lymer de posits
72
10 s >2400 on the fibre surface. Kan et al. have also
30 s 2000 demon strated the application o f three non-
60 s 900 po lymerizing gases-oxygen, nitroge n and a mixture
180 s 60 of 25 % hydrogenl75 % nitrogen gas-- through low-
temperature pl as ma treatm ent. The res ults of /la, /lw
Helium/a rgo n plasma and OFE are shown in Table 7 . The /la and /lw values
10 s > 1800
of th e low-temperature plasma (L TP) treated wool
30 s 150
fabrics increased, but the OFE values decreased. Th e
60 s 10
<I
inc reased /la and /lw values are probably du e to the
180 s
LTP etching on the fibre surface, res ultin g in surface
wettabi lity to water than acetone/argon plasma. roughn ess and hence altering th e coefficient of
Although wool does not wet easily because of its friction of the fibre . T he reducti o n in OFE is regarded
hyd rophobic epicuti cle layer, but the fabric treated as a factor in lowerin g the feltin g tendency o f wool.
with atmospheric helium/argon plasma over 60 s The density (0 ) of the felted halls revea ls that the 0
 BAJAJ: ECOFRIENDL Y FINISHES FOR TEXTILES
Table 7 - The f.\". f.\ w and DFE values and felted ball density of
the fibres 72
Sample/plasma f.\a f.\w DFE Felted ball density (D)
% g/cm'
Untreated 0.35 0. 16 37.3 0.064
PO (Oxygen) 0.49 0.30 23 .7 0.022 (1 65.6%)"
PN (Ni trogen) 0.50 0.31 23.4 0.019 (1 70.3%)"
PM 0.51 0.32 23.4 0.019 (170.3 % )"
(Hydrogen/nitrogen.
25 % :75 '70 )
"Values ill parentheses indicate % decrease in felted ball dens ity.
values of the LTP-treated samples are much lower.
The PN and PM treatments show the same decrease in
D values, which is better than the PO treatment. These
changes are th e same as observed in DFE results,
which confirm that th e DFE and the ball felting are
related to each other. Based on the res ults of /..l values
and DFE, it may be concluded that the nitrogen
plasma and gas mixture plasma impart similar anti-
felting effects to wool fibres and that their effects are
sl ightly better than the innuence of oxygen.
Ryu et al. 7 } used corona discharge for surface
modification of wool fibres and fabrics. An electron
spectroscopy for chemical analysis (ESCA) was done
to elucidate the changes in chemical composition on
the fibre surface. The corona discharge incorporates
oxygen atoms into the fibre and increases wettability
and laundry-shrink resistance of wool fabrics, but the
effects are smaller than those from low-temperature
oxygen plasma. It may thus be concluded that the
plasma treatment is a good alternative to chlorination
pretreatment in Hercosett process of shrinkproofing of
wool.
The effect of glow-discharge polymer treatments
on the shrinkage behaviour and physical properties of
wool fabric has been studied by Zuchairah et 01.74. In
this work, four different polymer sys tems, viz.
BasolanSW (cationic polyether in isopropanol
so lution, BASF), Basolan MW (weakly cationic
aminofunctional polysiloxane microemuls ion , BASF),
Polymer G (cationic amide-type res in in aqueous
solution plus polyethylene wax emulsion as softe ner) ,
and Polymer PL (cationic acrylic copolymer in
aqueous solution, ICI Stelco), are applied onto
plasma-treated wool fabric to enhance the degree of
shrink resistance. The leve l of shrink resistance varies
sign ificantly with plasma polymer treatments,
depending on th e kind of polymer sys te ms applied,
with Polymers PL and G conferring excellent shrink
175
resistance even for very short plasma pretreatment
times of 2 min. The extent of weight loss during
washing is also minimized for all plasma-polyme r
applications relative to polymer-only or chlorinated-
polymer treated wool.
5.2 Surface Modification of PET and Polypropylene Fibres
Tsai et al. 75 have reported some encouraging
results from the plasma surface treatment o f
polypropylene meltblown nonwovens in the UTK
one-atmosphere glow discharge plasma reactor. Thi s
reactor generates a large volume (up to 2.4 litres), low
power (less than 150 watts) , and uniform glow
discharge plasma in a parallel plate configuration with
oval electrodes of 23 I cm 2 face area, the lower
electrode being covered with a 3.2 mm thi ck
insulating Pyrex surface. The plates are set up in an
enclosed box that makes it possible to control th e
working gas used, and the spacing between the plates
can be varied. This reactor is energized by a custom-
made high impedance kilohertz power supply capable
of supplying up to 5 kilowatts of kilohertz power at
RMS voltages up to 10 kY, and over a frequenc y
range of 1-200 kHz.
Tsai et al. 75 used two groups of working gases, CO 2
and CO 2 + O 2, to treat the webs of PP at different
electrical and temperature conditions. Using CO 2
alone at a driving frequency less than 2 kHz would
not make the webs wettable, while using the mixture
of CO 2 + O 2 as working gas could make the webs
wettable if treated at low temperature for I min (Table 8).
Shisho0 76 and Sarmadi et ol.77also reported the
increase in surface energy for PP and PET samples
after plasma treatment, confirming the presence of
polar groups on the polymer surface and thereby
decreasing the contact angle. Such low- temperature,
low-pressure plasma treatment is effective in inducing
polarity at th e surface vis-a-vis hydrophillic surface
layer. Thus, it can reduce the high consumption of
chemical wetting agents normally required III
chemical processing of textiles.
Grafting of PP fabrics under AN-RF plasma was
carried out using ground pressure of 0.05 mm Hg , 0 .3
mm Hg pressure in the reactor and 60W and 100W
RF power. Reaction time was varied between 30 sand
5 min77 .In polypropylene, the plasma is generated by
inductive coupling in a tubular shaped argon container
and needle valve system permitted acrylonitrile (AN)
176 IN DIAN J. FIJ3R E T EXT. RES., MARC H-J UNE 200 1

Tabl e 8 - Plasma Irealmenl" o r 100 g/m2 me ii-blow n PP webs75

Sample Trealme nl lime Yo lwge Freq ue ncy Work ing gas Gas le mp. Crili cal sur Face lension, dy nes/cm
No. min kY rrns kH z C Orig inal I day 2 days

I 9.32 1.2 CO!, alb 21 70. 1 60.5 58.4

2 2 9.4 1.2 CO!, alb 21 71.2 66.2 64.2
3 3 9.4 1.2 Cal. 0/ 22 7 1.2 7 1.2 68.0
4 I 9.6 1. 2 Cal, 0/ 54 71. 2 60.5 58.4
5 2 9.4 1.2 CO!. O!e 54 7 1. 2 60.5 58.4
6 3 9.35 1.2 CO!. O!e 55 71. 2 60.5 58.4
7 I 9.52 1.2 CO! 54 58.4 56.3 54.9
8 2 9.52 1. 2 CO! 53 58.4 58.4 54.9
9 3 9.52 1. 2 Cal 54 58.4 58.4 56 .3
10 I 8.82 1.5 CO! 21 58.4 56.3 54.9
II 3 8.8 1.5 Cal 21 60.5 58.4 56.3
12 2 8.92 1.5 Cal 20 58.4 56.3 56.3
"Fabri cs we re Ireal ed al atmospheri c pressure.
Space gap helwee n e lec lrodes =2. 7 mm , Pyrex Ihi c kn ess =3.2 mm.
hYo lullle ralio (CO!:O!) =85: 15
' Yo luille ralio (CO!:O!) = 88.6: I 1.4

to now into the reacti on vessel. The va pour press ure
of the AN is above the operati onal reactor press ure
and co nsequcntl y th e monomer is easi ly fed in gas
form to the reacti on chamber under vac uum .
PAN surface graft ed PP fabri cs ex hibited imp roved
water absorpti on and dyein g properti es du e to th e
presence of nitrogen and carbon based un saturated
linkages and formati on of seco nd ge nerati on -C=O
prcdomi nate und er certain ex peri men tal conditions.
Others have also reported that ammoni a plasmas do
not produce primary amin e effi cie ntl y, and
consequ entl y saturated and un saturated amin es have
bee n proposed in order to create reactive surface
amin e groups.
5.3 Water Repellency and Surface Dyeing of Polyester Fabrics

groups. Effici ent graftin g takes place eve n in short
treatment times.
Reactive amin e group implantati on on polymer
surface by cold pl as ma reacti ons also represe nts one
of th e possibilities for surface fun cti onal iza ti on. One
approach for att ac hing reac ti ve amin e groups is to use
ammoni a plas ma. Ca rba ugh cf a/.78 have studi ed th e
pl as ma decompos iti on of ammonia and ha ve proposed
th e foll ow ing mec hanis m:
NH1--+ NI-i' + H
H + NI-I,1- -+ NH z + 11 2
11 2 --+ 2 I-I
2 NI-I 2--+ :NH + NH1
2 NI-I 2--+ N2H4
2: NH--+ N2+H 2
It is sugges ted th at the primary amin e radi cal s are
most likely th e entit ies to do min ate th e reac ti on
mec hani sms and co mbine with surface radi ca ls.
Howeve r, because of th e coex istence of a signifi cant
!l umber of mo no- and multi -rad ical spec ies and
va ri ous reacti on poss ibilities in th e plasma stat e, th e
molecul ar frag ments other tha n NI1 2 can al so
Po lyes ter fa bri cs 7,) have also bee n successfull y
tre ated with O 2 or CF4 plasma under di ffe rent power,
press ure and time co nditi ons. Elec tro n spectrosco py
for chemical analys is (ESCA) clearly indicated th e
surface ox idati on and nuoridati on. Oxyge n plas ma
trealment im proved both water upta ke and sur face
dyeabi lit y, 'v" hil e CF~ plas ma trea tme nt improved
wal eI' repellency along with im proved surface
dyeabi lit y with c. 1. Bas ic Blue 3.
Unex pec ted su rface dyeabilit y with a basic dye and
... ( I )
wat er repell ency effee ts ont o CF4 plasma trea ted PET
... . (2)
fabric s have bee n related to inlense nu ori da ti on
(3)
leadin g to tenon-l ike surface and simult aneo us
(4)
un sa turat ed bonds and trapped free radi cal s. The
(5)
mechani sm of th e reacti ons fo r two ty pes of gases, O 2
(6)
and CF~, in th e discharge sys tem is as foll ows:
In O 2, a mi xture of ac ti ve oxyge n spec ies is
produ ced in th e discharge cham ber. Some of the
reacti ons whi ch are beli eved to occur are:
O 2--+0+ 0 (7)
0+0--+ 0 2 (8)
02'~ 0 2+ hv (9)
 BAJAJ: ECOFRI ENDL Y FINISHES FOR TEXTILES 177

CF4 di ssoc iates in the first step accordin g to the In another study, wool , silk, nylon 6 and chinon
following equation: (promix) fabri c dyed with c.1. acid Black 155 were
CFc ----. CF, + 'F .. . ( 10) subj ected to sputter etching and also exposed to a
In the prese nce of an orga ni c polymer surface, low-temperature argo n plasma. A large number of
th ese radi cal s will resu lt in surface nu orin ati on: small microc raters (s mall er than the wave length of
RH+F~ - R F+ H ' ( II ) vis ible li ght) were form ed whi ch considerab ly
R+ 'CF3 ~ - RCF3+H ( 12) reduced the renecti on of incident light, and hence
' R+CF4 ~ - RCF3+F (1 3) increased the depth of the shade. On th e oth er hand,
'RIl + 'RIll --'RnRIll ( 14) low-temperature argon plasma treatment did
Surface nu orinati on as show n 111 Eq.12 or incorporat e oxygen atoms onto the surface but the
nu orocarbon graftin g can occ ur by mechani sm of physical changes we re negli gible.
chain transfer from a radi ca l of CF4 to the ac ti vated Yoon el 0 1.56 also reported the mechanical and
fibre. Plasma- induced sur face stru cture modifi cati ons dye ing pro perti es of wool and cotton fabrics treated
were monitored by photoelectorn spectrosco py an d with low-temperature plasma and enzy mes. Pl asma-
electro n spectrosco py for chemi cal anal ys is (ESCA). treated cotton shows reduced strength , but the rate of
A hi gh oxyge n to carbon (OIC) indicate hydrophili city, we ight loss in subsequent cellulase treatment
and hi gher nuorine to carbon ( F/C) atomi c rati o values decreased . The rate of dy eing with a direct dye also
of plas ma-treated fab ri cs indicate hydrophobicity.
increased in th e foll owin g order:
In anoth er stu dy, Oktem et al. so reported th e
Plasma-treated cotton < untreated cotton < cellul ase
modi ficati on of po lyester fabrics by ill- sit II plas ma or
treatment == plasma/cellulase combination.
pos t-plas ma polymeri zati on of acryli c acid . Fabri cs
were direc tl y treated in acry li c ac id pl as ma in one set
Table 9 - 0 1 va lues o f se veral plasma/mo no mer-trea ted
of ex periments, while in th e oth er set of ex periments,
polyester sam ples and co nditi ons o f trea tme nt8~
th ey were first treated in argo n plas ma and th en Mo no mer Power Pl asma d urat ion 01
immersed in an aqu eo us ac ryli c acid bath . The second W mi n %
method resulted in better dyeability and soil No ne (Untreated polyester) 22.2
repell ency in con trast to lower surface we tt ability. Plasma in vac uum o nl y 20 60 20.0
Anti-soiling of polyes terSI was also ac hi eved by HMDS 20 60 19.5
direct current an d radi o freq uency plas ma treatm ent of Tct rac hl oroeth ylcne 20 60 2 1. 8
diffe rent durati ons . The soil repell ency increased Plas ma in vac uum o nl y 30 10 2 1.1
1, 1-2-Tri ch loroetha ne 30 10 21.4
with the increasing durati on of treatment. Tric hl oroc th ylene 30 10 21.1
Cold plasma treatment of polyester fabri c in A ll y l"minc 30 10 21.1
presence of several vo latil e monomers82 containing Pl as ma in vac uum o nl y 40 5 22.2
name retardant was studi ed. It is interes tin g to note T ric hl o roc th yle ne 40 5 2.2
th at oxyge n index va lues for all pl as ma- treated
samples was found to be so mew hat Jess th an th at of
Untreated polyester fabric
virgin materi al (Tabl e 9). However, th e burnin g rates
were found to decrease considerably, spec ificall y in 10 Pla sma treatment under vacuum o~ny
hexamethyldi siloxane (HM OS) plasma-treated fabri cs c: 0 Tetrachloroethylene plasma-treated fabric

(Fig. 8). 'E 8 tJ HMOS plasma-treated fabric

5.4 ElTect of Plasma Treatment on Oyeability of Wool, Nylon ]E 6

:l
.0
~
and Cotton
Wa kida et 0 1.83 also demonstrated th e effec t of !c; I.

oxygen low-temperature plas ma treatment of wool 0::

and nylon fibres on the dye ing rate and saturation dye 2
ex hausti on of ac id dyes des pite increased
o~----~----~------~----~------~
electronegativity of the fibre surface with th e 19 20 21 22 23 24
treatment. The dye ing rate of th e pl as ma-treated woo l Oxygen, %
also increased considerabl y with natural dyes such as
Fig. 8 - Rat e o f burning as a fun cti o n o f enviro nment,,1 oxygen
cochineal, Chinese cork tree and madder, but not with
co nce ntrati o n fo r untrea tcd po lyester fabric a nd pl as ma trea ted
gro mwe ll. fabric at 20W, 60 min (re f. 82)
178 INDIAN J. FIBRE TEXT. RES ., MARCH-JUNE 2001

However, the oxygen plasma treatment onto wool Table 10- Rrepresentative bacteria used in evaluation of
improved its strength and resulted in higher rate of antimicrobial ac ti vity of modified fabr ics
weight loss in the subsequent protease treatment and Species Resulting End-use
increase in dyeing rate. e ffectld isease
84
Vohrer has also indicated the importance of Gram-positive bacteria
glow~ischarge treatments for surface modification of
StaphylococclIS aureus Pyrogenic infections Hyg ienic, medical
technical textiles Staphylococclls Body odour Aes thetic
epiderlllidis
6 Antimicrobial Finishes85 lOJ Co rynebacterilllll Body odour Aesthetic
diphteroides
Antibacterial finishes are germicides applied to
fabrics to prevent odours produced by bacterial Fungi
decomposition, such as perspiration odours, and also Candida albicans Diaper rash Hyg ienic
to reduce the possibility of infection by contact with EpIdermophyton Infection of skin Hyg ienic
contaminated textiles. Fabrics may also be treated .flocco.wlIl and nail s
Trichophyton Athletes's fo ot Hyg ien ic
with germicides to prevent mildew, a parasitic fungus
interdigitale
that may grow on fabrics that are not thoroughly Trichophyton rubrulll Chronic infecti ons Hyg ienic
dried. Both mildew and rot may be controlled by of nai Is and sk in
treatment with resins .
85 Vii-uses
Natural fibres in particular are prone to attack as
they are readily digestible by bacteria a nd fungi, but Poliolllyelitis virus Poliomyelitis Medi cal
Va ccinia virus Localized disease Medical
synthetic fibres are not completely immune either, induced by
especially with the growth of specialty finishes, many vaccinati on aga inst
of which can provide an important growth medium smallpox
for the denizens of the microscopic world, enabling
Protozoa
them to gain a foot hold to break down the
Tricholllonas vag inalis Trichomoniasis Hygie nic, medical
manufactured fibres. Representative bacteria used in
vaginitis
evaluation of antimicrobial activity are listed in Table 10. Trelllatode (blood Hygienic, med ica l
The protection of cellulosics and manufactured .flllkes)
fibres or fabrics to control the growth of bacteria can Schistosollla japoniculII Sch istosom iasis Hygienic, medi cal
be accomplished by:
and the change in conditions of the medium are
a finishing process in which an antibacterial
shown to affect the decrease in the tensile strength.
additive is fixed on the surface of the material by a
As shown in Table 11, the microbial growths were
res 111 ,
differently inhibited by several finishing chemicals,
grafting of antibacterial agents on the cellulosic
but most of them were removed by washing 85 .
chain, and s7
Cotton fabric and partially carboxymethylated or
incorporating agents into the spinnin g solution of
cyanoethylated fabrics were treated with g lyoxa l
manufactured fibres.
86
using ZnCI 2.6H 2 0 and AI 2(S04h. 18H 20 as catalysts
The finishing process is the technique most in the presence and absence of a sil icon elas tomer.
frequently employed to impart antibacterial activity to The fabrics so treated were mo nitored for dry crease
cel lulosic textiles. However, the durability to recovery and retained strength properties after so i I
laundering achieved by this techn ique is usually not burial for two a nd four weeks. Results obtained
as good as that obtained by grafting or incorporation indicated th at while the cotton fabric undergoes
during spinning. Th e damage caused by micro- complete decay after two weeks, the cyanoethylated
organism s to 100% cotton under di fferent conditions cotton samples having 2.01 % N retain ed 24.45 % and
has been studied in-depth, when different finishing 37.33 % of their tensile strengths after two and four
materials were used. The damage caused by weeks of so il burial respectively. This was against the
Aspergillus niger, used as th e experimental organism retained strength of 98.27 % and 74.73 % after the
for 100% colton material, was seen as a decrease in cyanoethylated cotton was given glyoxal treatment in
the tensile strength with time, temperature and pH , presence of aluminium sulfate and silicon e lastomer.
 BAJAJ: ECOFRIENDLY FINISHES FOR TEXTILES 179

Table II -Antibacteri al chemicals85 beneficial effects are highly durable even after 50 use-
Name Chemical nature Compo- wash-use cycles. The antibacterial effect, both in
sition formulation and on treated materials , has been
gIL affirmed by extensive hospital field trials .
Afrotin LC Na salt of a heterocycl ic compound 20 Magnesium peroxide-based new antibacterial
Mystox ELN Pentach loropheny llaurage and non- 2.5 agents (derived from 28: I mole ratio of H 20 2:
ionic emulsifying age nts
Mg(OAchAH 2 0 with a peroxide content of 24%) and
Mystox WFE Aqueous solution of sod ium-o-
phenylphenate their applications on cellulosics have been described
Antibac MF An organic compound containing 40 by Vigo et al. 89 . They reported several advantages
nitrogen with no halogen or heavy over previous antibacterial agents derived form the in
metal salts
Antibac MFB Combination of heterocyclic organic 80
situ application of zinc or zirconyl acetate/hydrogen
compounds peroxide systems applied to textiles. Cotton fabrics
Fungitex OP Derivatives of benzimidazole 100 had much better affinity and durability of the affixed
Table 12-0dour and bacterial counts of towelling 91
agents than cotton/polyester blends or all sy nthetic
Treatment Odour Bacterial count fabrics such as polyester, polyamide and
CFU/mL polypropylene.
90 9t
None Very stron g, > 10 10 A new antimicrobial treatment . , called
pungent odour Reputex TM20, has been found to be a durabl e finish
Softener only Very strong, 2.6x 109 for cotton and cotton blends, based on active agent
pungent odou r
poly(hexamethylene-biguanide hydrochloride) PHMB
0.2 % PHMB No odour 6x 105
Softener and 0.2% PHMB No odour 4x 104 (Fig. 9). It is readily applied by padding or
exhaustion. The antibacterial efficacy of th is
treatment on fabric has been assessed USlt1g
() C~ qualitative agar plate and quantitative bacterial

l
NH NH2
counting methods (Table 12). Treated cotton is
-CH2 CH2 CH2 II CII
C CH 2 CH 2 CH 2 -
bactericidal for approximately 25-50 wash cycles,
"'-/"'-/"'-/ depending on the wash conditions .
N N N
H H H Bacteria-contaminated fabrics 92 in hospital s are
Average n : 12
known to be a major source of cross infection . Post-
Fig. 9-Structure of PHMB , the active agent in the antibacterial operative infections are the most common hospital
treatment (ref. 91) acquired infections since bacteria can, by a variety of
routes, find their way into an open wound and cause
Graft or ill-situ polymerization of acrylates onto sepsis. Post-operative wound infections develop in 2-
cotton and rayon in conjunction with zinc or copper 5% of patients undergoing surgical procedures.
salts produced fabrics with durable antibacterial Surgeons gowns and drapes used to surround the
activity. Cotton fabrics resistant to Staphylococcus operative field should be effective aseptic barriers
epidermidis for 50 launderings and to Staphylococcus between the underclothes of the surgeon and the
aureus for 25 launderings were produced by in situ aseptic field and between the patient's body other
polymerization of zinc acrylate, zinc methacrylate and than the prepared area and the sterile field. In the
zinc itaconate. Grafting of acrylic acid onto operating room, however, liquids such as blood, sweat
and saline solutions can cany bacteria with them, and
mercerized cotton and rayon followed by immersion
if a liquid is wicked from a surgical gown to a non-
in copper sulphate imparted durable antibacteria l
sterile surface, one or both sides will become
activity against Staphylococcus aureus and
contaminated. In an operating room, a patient's blood
Escherichia coli. can penetrate surgical gown material and probably
SITRA 88 has also developed a chemical finish for contaminate the surgeon's skin if not well protected.
yarn, fabrics and garments named as SANTIMIT Several researchers have used antimicrobial
(SITRA Antimicrobial Textiles) which possesses finishes to provide fabrics with barriers against micro-
93
almost complete antibacterial potentiality against all organisms . Morris et al. used an antibiotic as an
major diseases and perspiration odour. These antimicrobial agent to impart antimicrobial properties
180 INDIAN J. FIBR E TEXT. RES ., MARCH-JUNE 2001
to cotto n. They found that fabrics treated with
antibi otics retain excell ent bacteriostatic activity.
Points and Wadsworth'J4used a f1uorochemical as a
repellent finishing agent on spun laced non woven
fabrics. The surface tension of blood and body fluids
ranges between 42 and 60 dyne/cm; to maintain blood
repellency , the surface tension of fabrics has to be
much lower than th at of blood. In order to provide
100% cotton fabric and 55/45 wood pulp/polyester
spun laced nonwoven fabric with barriers against
micro-organisms and blood, the samples were treated
with gentamicin, a broad-spectrum antibiotic, and a
f1uorochemical compound using pad-cure method.
The antimicrobial activity of the sa mples was
analyzed quantitatively by measuring the number of
colonies of Klebsiella pneulllonia and qualitatively
using the parallel streak method with Stapli ylococcus
aureus. Blood repellency is assessed with spray and
impact penetration tests using both synt hetic and
human blood. Samples treated with both the antibiotic
and the f1uorochemical (dual fini sh) show a high
reduction rate in the number of colonies grown and
clear zones of inhibtion.
Dual finished specimens treated with 1.1%
ch itosan concentration also maintain over 90%
reduction in the number of colonies. The blood
repellency of dual finished nonwoven fabrics is
superior to that of dual fin ished cotton . As regards the
mechanical properties, the bending rigidity and shear
rigidity increase when cotton and nonwoven fabrics
are treated on ly with chitosan, but these properties
decrease after the fluoropolyme r treatment. Air
permeability of the specimens decreases slightly afte r
the dual fini sh.
96
In another study, chitosan of specific molecular
weight has been used for its antimicrobial activity.
Protonated amine groups in chi tosan inhibit the
growth of micro-organisms by holding negatively
charged micro-organism ions . However, the
insolubility of chitosan in neutral or alkaline
conditions Ii mi ted its app lication.
Many antimicrobial finishing agents co ntain
quaternary ammon ium groups and attac hin g such a
group to ch itosan cou ld improve its antimicrobial
activ ity. Possibly , the aqueous solubility of a
quaternary ammoni um deri vati ve of chi tosan, for
example Glycidyltrimethylammonium ch loride
(GTMAC) as shown in Fig.1 0, would further increase
and improve its use as an antimicrobial finishing
agent.
CH3
1+ _
+ CH2 - CH -- CH2 - N - CH3 CI
...... 0/ tH3
GTMAC
Fig. IO - Reacli on sc he me for sy nthes is o f l-lTCC (re f. 96)
Preferential reac tion of GTMAC with amine
groups in chitosan under neutral or alkal ine conditions
produces N-(2-hydrox y )propy 1-3-trimethy lammoni um
chitosan ch loride (HTCC) (Fig . I0). At very low
concentration% of 0.025 % owb, HTCC shows
superior antim icrobial activity indicated by an almost
100% bacterial reduction, whereas 1% owb chitosan
shows only 30% bacterial reduction. Since HTCC is
so luble in water, th e application of a non-ionic binder
cons iderably improves the laundering durability of
HTCC-treated cotton .
Citric acid (CA) and chitosan'J7 are used as durable
press and antimicrobial finishing agents for cotton and
are applied by means of the conventional pad-dry-
cure process. CA is expected to react with hydroxyl
gro ups in cellulose and chitosan or with amino groups
in ch itosan to form ester crosslinking or an inter-ionic
attract ion. Durable press ratings of 3.5-4 are obtained
with CA and chitosan treatments. The durable press
performance is retained through twenty washings and
tumble drying cycles. Strength retention improves
more wit h CA and chitosan than with CA alone.
Durable and regenerable antimicrobial cellulose-
containing fabrics have been deve loped recently
based on a theoretical regeneration model proposed
by Gagliardi in 1962. In this new techno logy , th e
precursors of biocidal compounds, in stead of the
biocides themselves, have been used in the chemical
treatment of cellulosic materials, which successfully
demonstrated an innovative approach in preparing
regenerable funct ional materials,!8 The functional
agent used in the chemical treatment is a hydantoin
deri vat ive, monomethy 101-5 ,5-dimethylhydantoin
(MDMH or Anti- I), a bifuncti onal compound
possessing one side reactive to cellulose and anoth er
to act ive chlorine to form a halamine bond (Fig. II ).
The durable and regenerable ant im ic robial function of
 BAJAJ: ECOFRIENDL Y FINISHES FOR TEXTILES 18 1

Cellulo se Table 13 - Biocidal properties of COllon fab ri cs processed under

~ diffe rent pH and dwell tillles 98
OC H2
\ CH3 Bleach ing pH Dwelitillle Add-on Bioc ida l res ult against E. coli
N + CH 3
.Kill bacteria 111 in % After I was h After 5 or 8

O~ . /'O
N 2.50
I 4.65
H Hyda ntoin rings
Fig. II -Reaclion of MDMH (lllonolllethylol-5,Y -
di lllethylhyda ntoin ) wit h ce llulose (ref. 98)
the treated fabric is attributed to the reversible
ox idati ve properti es of cyclic hal a min e stru ctures. Th e
effectiveness of th e antimi cro bi a l fabrics is re lated to
the amo unt of active hal a min e agents in corpo rated
o nto the fabric s .
The bi oc idal functions on the fabrics are achieved
by two ste ps of c hem ica l process in g including
fin ishing under acidic co nditi o ns a nd rinsing with
chlorine bleach . Each of th e processes may have its
ow n impact on physical properties of the fabric .
Chemical fini shin g of the hydanto in compound o nto
ce llulose was perfo rmed unde r acidic conditions that
are quite harmful to the chem ica l structure of cotton
ce llul ose. Active chl ori ne in bleaching so luti o ns
usuall y damages th e te nsil e stren gth of fabrics due to
its ox idative pro pe rti es. T hese fac tors, affecting th e
mechanical properti es of the treated fabrics , should be
investigated to e nsure the appropriate properti es of the
antimicrobial fabrics. Bioc idal prope rti es o f cotton
fabrics processed under different pH are g iven in
Table 13.
Biosil 9<J fini sh e mpl oys an agent which joins
quaternary ammonium salt with organosilicone . By
graft-poly merizin g with fibre, thi s o rganos ilicone is
affixed to fibre firmly. For thi s reason, the agent does
not leach out even by washing. Th e quaternary
ammonium salt destroys cell membranes o f bacteri a.
Bi os il is also characterized by the fact that there is no
harmful influence res ultin g from the oozing of the
agent. [n princ ipl e, "Episca ll" a lso employs
qu aternary ammonium sa lt as a base. Toyobo has
deve loped " Epi scall " as a genera l purpose type of
" Biosil". "Epi sca ll " can be treated to any fibre, as is
th e case with " Biosi l" . T oyobo has ado pted "Biosil",
however. mainl y for cotton tex til es, while " Episcall"
is for all tex tiles. The employed agent, nam ely " Dow
Corning 5700" (s ilico ne quaternary ammonium salt),
sati sfies stri ct criteria issued by th e U.S. Environment
Pro tecti o n Agency (EPA) and a g uarantee is g ive n to
its safety as we ll.
was hes
30 2.83 > 5111111 Kill all
30 1.42 > 2111 111 >3 111 III
2.47 5 2.88 > 1 III III Kill all
4.56 5 1.64 >2 III III >3111111
" Biosil" and "Episcall " finishes have recei ved
acceptance not o nly for underwear and foundati ons
worn in direct co ntact with the skin , but also
freq ue ntly in th e sec tor of work wear and sportswear
w ith th e ir hi g h occ urre nce of sweating. Bacteria-
resistant/deodorizing fini shes such as " Bi os il" and
" Episcall" have beco me indi spe ns ibl e for socks and
panty hose as we ll.
In addition to after-fini shin g, there are other
products with knead-in bacteri a- resistant agents fo r
syn thetic fibre, which can bring about similar effects.
T oyobo has developed and commerciali zed
" Feelfresh" (acrylic fibre) and "B ioguard-N " (nylon
fi la ment) .
Kanebo loo launched an antibacterial nylon fire
" Li vefresh-N ". Thi s fibre is the first o ne made w ith an
ino rganic antibacte rial additive Ag-zeolite kneaded in .
" Livefresh-N " is used in the fi e ld of innerwears
including lingeri es and hos iery . But there were
pro blems such as yarn breaks in di fferent processes
and yellowing when exposed to heat a nd li ght.
Especially, nylon polymer has a re markabl e yellowin g
compared with other po lyme rs. In stead of Ag-
zeo lite 'O' , it has slow re lease g lass phosphate wi th
silver ions as an a ntimicrobial additive kneaded into
fibres. This enabled to maintain antibacterial effect
with less amount of additive. At the same time,
yellowing defect was improved by far.
6.1 Bacteria-Resistant Finishes: Escola and Epicomodo
In contrast to bacteria-res istant/deodorizi ng
finishes, which reduce th e g row th of bacteria to
prevent the generation of odors, bac teri a-resistan t
finish gives more priority to the e ffect of prev entin g
g rowth of germ s.
For so me time, the attention has been focussed on
Methicillin-resistant Staphilococcus aI/reus
(MRSA)I02. Abu ses of antibiotics have produced a
mi serabl e si tuati o n in which a ntibi ot ic-resistant
mi crobes have grow n conversely and there is no way
fo r medic al treatme nt. M any devices have been
182 INDIAN J. FIBRE TEXT. RES. , MARCH-JUNE 200 1
employed in the forefront of medical treatment and
responsive actions have been progressing against
MRSA . Moreover, actions were requested even for
clothing such as uniforms and interior goods such as
curtains to prevent the transmission of germs, along
with the steri li zation of everything which is used at
hospitals, in order to prevent hospital infection .
"Epicomodo" is a fabric which Toyob0 99 has
developed to cope with MRSA, since it has become a
serioius task to keep a clean in-hospital environment.
Toyobo has proposed 100% polyester, polyester/
cotton blends and other fibres in a number of
combinations for curtains, white coats and bedding
used in hospitals. The mechnism of bacterial-resistant
fini sh used for Epicomodo is as under:
The agents with positi ve ions attract germs to their
environment by acting upon their cell membranes
with negative ions to control the activity of the germs
by destroying cell membranes as shown in Fig. 12.
One bath process for dyeing and simultaneous
antimicrobial finish by methanolic extract (1-5 %) of
Tulsi leaves (OCillllllll sallctulII) on cotton l03 has been
investigated. It is believed that urosolic acid
(C30H4s0 3) is the active ingredient which inhibits the
growth of several strains of Staphylococci.
7 Waterproof Breathable Fabrics HJ.I.I12
Waterproof/moisture permeable fabrics from
several sy nthetic fibres have been designed for
skiwear, track suits, rainwear, and mountaineering
clothing.
Light weight fabrics coated with poly(vinyl
chloride), polyurethane and other sy nthetic rubbers
have become increasingly popular for foul-weather
clothing. Although garme nts manufactured from these
fabrics provide excepti onal protection against rain
and, to a less extent, wind penetration, but
considerable build-up of moisture vapour inside the
This portion will burst
A /---),--G
~-
1\!icrobial ........
conlrolling_ _ _ _ _...-.!~__..._I1I....-II~- controlli
ag~ nt
Fig. 12-Bacterial -resistant mec hani sm of picolI/odo (ref. 99)
clothi ng may cause discomfort. Thi s problem arises
because of the water-vapour impermeability of the
polymer coating.
To overcome this problem, breathable polymer
coatings are now available th at have made possible
great improvements in the comfort of this type of
clothing.
7.1 What is a Breathable Fabric ?
A breathable fabric is waterproof and breathable
because of the enormous size difference between a
water droplet and a water vapo ur molecule 1ol . The
former is 100 J..lm in diameter whereas the latter is
0.0004 J..lm, i.e. there is a factor of around 2,50,000
between the two sizes. Microporous
polytetrafluoroethylene (PTFE) Gore-lex laminates
have been successfully introduced as breathable
fabrics. Comparative assessment of Gore-tex and
Neoprene vapour barriers in fire fighter sui ts has also
been made.
7.2 Classification of Breathable Fabrics
The breathable fabrics can be classified into three
main categories:
7.2.1 High-density Woven Fabrics
High-density wovens owe their breathability to the
densely woven, thin and smooth yarns that are usuall y
made from microfibres. This type of weaving results
in a windproof fabric with an excellent water vapor
permeability compared with laminates and coatings.
Its water impermeability is, however, not very high ,
even though a water-repellent finish is usuall y
applied. The major advantage of these fabrics is their
good grip. For those applications where grip, water
vapour permeability and windproofing are more
important than water impermeability, marvellous and
fashionable clothing can be made from these fabrics;
they can be found in ski clothing.
(refer to B)
B
Thi s germ exploded
1
agent
Fibre
 BAJAJ: ECOFRIENDLY FINISHES FOR TEXTILES
7.2.2 Laminated Fabrics
The fabric can be of almost any desired
construction. Lamination of the film on a fabric uses
special adhesives, sometimes even breathable ones. If
non-breathable adhesives are used , care has to be
taken not to cover the whole surface in the coating
process. This process can be done in rotary-screen-
printing, spraying or web-lamination.
The banier film can be microporous, e.g. Gore-Tex
and Microtex. Breathable films are made through
biaxial stretching process of Teflon film by
mechanical fibrillation.
For certain polymers, biaxial stretching produces
microscopic tears throughout the membrane, which
imparts a suitable microporou s structure. For
example, PTFE membranes are used in the Goretex
two-l ayer and three-layer laminates. The thin
microporous membrane is made from solid PTFE
sheet by novel drawing and annealing process. In
drawn form, the tensile strength is increased three
folds. The manufacturers claim that these PTFE
membranes contain approximately nine billion pores
per square inch, with pore volume of up to 80% and a
maximum pore size of 0.2 11m.
Hydrophilic polymer film can be extruded or cast
from such polymers havin g polar groups which can
absorb, diffuse and desorb water as vapour, e.g.
Sympatex film (polyester) developed by Akzo.
Bion II film (polyurethane), a product of Toyo
Cloth, and Excepor-U (polyaminoacidlPU), a product
of Mitsubishi-Kasei, have also been used as moisture
vapour breathable films .
Thintech is a film of 3M in which a polyolefin
(microporous matrix) is impregnated with hydrophilic
polyurethane.
Thermoplastic elastomers such as copolyether-
esters (PEE), having alternating hard polyester
segments and soft polyether segmen ts, and polyether-
polyester block amides (PEBA) have also been used
as breathable films for protective clothing.
7.2.3 Coated Fabrics
7.2.3.1 Microporous Coatings
The microporous barrier layers breathe primarily
through a permanent air permeable pore structure.
Diverse techniqu es have been used to manufacture
microporous coatings. The most important among
them are so lvent exchange, phase separation and
phase invers ion .
183
Solvent Exchange: In this process, a polymer
dissolved in a water miscible solvent is coated thinly
onto the fabric. The porous structure is developed by
passing through a coagulation bath where water
displaces the solvent. For example, the textile
substrate is coated with polyurethane solution where
DMF is being used exclusively as the solvent and the
fabric is passed through coagulation bath containing
water, where water displaces the solvent to give a
porous structure.
Phase Separation: The coating polymer is applied
from a mixture of a relatively volatile so lvent with a
proportion of higher boiling non-solvent. Precipitation
of the polymer as a microporous layer occurs as th e
true solvent evaporates faster during the subsequent
drying process. For example, Ucecoat 2000, a
polyurethane based coating, operates on this principle.
Here, a low-temperature boiling solvent (methyl ethyl
ketone) evaporates preferentially as the fabric passes
through the oven, thereby increasing the concentration
of the non-solvent in the coating. When the
concentration of the non-solvent reaches a critical
level, the polyurethane precipitates out in a highl y
porous form and the remainder of the solvent and the
non-solvent evaporate from the coating as the fabric
passes through the oven.
Phase In version : A solution of polyurethane
containing a non-so lvent is coated on a fabric. In a
selective evaporation step, the solvent is eliminated
first. The polyurethane then precipitates in a
microporous way. An example is Ucecoat 2000 (S) of
UCB Speciality Chemicals.
7.2.3.2 Hydrophilic Coatings
The polyurethane in solution contains hydrophili c
groups . After coating, the solvent is evaporated
leaving a monolithic (non-porous) layer on the fabric.
Examples are Ucecoat NPU series of UCB Speciality
Chemicals, Witcflex/staycool of Baxenden and
Impraperm of Bayer.
7.2.3.3 Microporous and Hydrophilic Coatings
A hydrophilic finish on a microporous structure is
used to upgrade the water-resistancy of microporou s
coatings. Care has to be taken to select a hydrophili c
finish that does not impart an unacceptable loss in
breathability. Ucecoat NPU2307 finish on top of
Ucecoat 2000 (S) microporous coating is an example.
A microporou s coating can be obtained by coating
the fabric with a foam. Thi s gives a rather cell
184 IN D IAN J. FIBRE TEXT. RES., M ARC H-J UNE 200 1

structure which has to be crushed . Breathability is
good but water-proofness has to be improved. An
example is Dicryl an system of Prersree/Ciba Geigy .
Performance of various breathable fabrics is shown in
Table 14.
7.3 Evaluation of Breathable Materials
The two most important characteristics of
breathable fabrics are water vapor and heat transport.
In order to gain an insight into the transient states of
such transport across a set of layers of fabrics, an MU
water vapor transport simulator (MU- WYT simul ator)
has been developed.
It ha<; been demonstrated that the water transport is not
in flu enced significantly by sUlface charactelistics-
the hydrophilic or hydrophobi c nature of fabrics. On
the other hand, when liquid water contacts a fabric ,
such as in the case of sweating, the surface wettability
of fa bric plays a dominant role in determining th e
water vapor transport rate th rough layered fabrics. In
such a case, the wicking characteristi cs, which
determin e how quickly and how widely liquid water
spreads out laterally on the surface of/or within th e
matrix of th e fabric , determine the overall water
vapour transport rate through the layered fabrics.
The overall water vapour and heat transport
characteristics of a fabric should depend on oth er
factors such as the water vapour absorbability of th e
fibres and the porosity, density and thickn ess of th e
fabric. The overall dissipation rate of water va pour
depends on both the vapour tran sport rate and the
vapour absorption by fibres, which are mutually inter-
related . Water vapour transport is governed by th e
vapour press ure gradi ent that develops across a fabri c
layer. When a fabric is subj ected to given
environmental conditions, th e ac tual water vapour
transport rate greatly differs depend ing on th e nature
of th e fibres , even when oth er parameters such as
density, porosity and thickn ess are nearly iden ti cal.
To understand thi s process more cl earl y, Robin
Howie from the Institute of Occupat ional Medi cine in
Edinburgh has developed a meth od for calcul atin g the
requirements that a breathable clothing should have
under specific conditions, by takin g the foll ow ing
parameters into acco unt 11 0 :

lll9
Table 14 - Brea thability determin ed from a co mparati ve wea rer tri al

Colo ur Fabric sa mp le Total we ig ht Water vapo ur pe rmeabilit y Wate rproo fn ess

coating g/m 2 (20C, 95 % RH ) (Hydrostatic Head)
UCB UCB
method I method 2

Green Standard non-breathable polyurethane 87 286 281 + 300 cm

Grey Hydrophili c PU 81 1120 2900 + 300 cm
Black Ucecoat TD 9627/NPU 2307 98 1290 4180 + 300 cm
Hyd rophilic PU
Blue Laminate: hyd rophili c po lyester film 145 1290 3470 + 300 cm
Red Ucecoat 2000 S 95 2 190 4240 + 300 cm
Mi croporo us PU
Purple Ucecoat 2000 S/NPU 2307 88 2230 4660 + 300 cm
Microporou s and hyd rophili c PU
Yell ow PTFE laminate mi croEorous 78 2 140 5870 + 300 cm
Table 15 - Fabric permeability requ ired to maintain eq uilibrium 110

Work rate Air fl ow ra te (1/m 2/min ) at WYTR" (g/m 2/24h ) at

10C 20C 30C 10C 20C 30C

Low 360 1020

Moderate 80 720 360 2076
Hi g h 320 1110 1392 3 156
Very hi g h 120 560 1470 640 2400 4 140

"Water vapour tran sm issio n rate

Assumpti ons: Intern al RH : 100%
Ex ternal RI-I: 50%
Intern al temp. : 33C
o
Ex ternal temp.: 20-30 C
Internal air exc hange: 50%
Ex te rn a l air speed: up to 4m/s
Garment th erma l resi stance : 1.4 elo
Wearer: 70 kg mun
Ga rment is o il impermeable
 BAJAJ: ECOFRIENDL Y FINISHES FOR TEXTILES 185

4000 po lymer contained less sorbed water. The

-E
VI

Q) 3000
"'mean

o Sympatex
o
x

Gore - Tex II
0.40 conce ntrati on-depe ndent behav iour has also been
studied . Two semi-impermeable membra ne laminates
(.) (Gore-tex and Sympatex) ex hibit concentration-
c: Gore - Tex III
C\l
iii 6, PTFE film dependent transport behaviour as co mpared to
'iii microporou s PTFE membrane.
Q)
a: 2000
c:
C\l
Q)
::2
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