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Ijftr 26 (1-2) 162-186 PDF
Ijftr 26 (1-2) 162-186 PDF
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
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 % %
1111
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 chelating agent and diluent for aluminium ions, thus
sulph ate, on heating g ives monoacetals and diacetal s moderating the tendency of the catalyst to degrade the
of glyoxa l with cellulose (Fig. I). Free aldehyde cellulose.
groups present due to the single-ended attachment of
glyoxal as in I in Fi g. I were found to be re movable 2.1.2 Mild Cure Process
by oxi dati on with chlorous acid or reduction with The addition of poly hydric alcohols in the pad bath
potassium borohydrid e. Since glyoxal mol ecule can results in low cure process with improved fabric
form four link ages to cellulose, glyoxal may be whiteness and increased DP ratings. Alpha-hydrox y
regarded as tetrafunctional. Magnesium chloride was acid was added as catalyst activator to suppress the
used as a catalyst in early studies for applying a very strength losses in treated cotton . This mea ns th e
hi gh g lyoxal concentration (10% by wt.). In th e curing temperature for crosslinking could be lowered
absence of active hydroge n compounds as co- reactive to lIS-125 °C. The order of effecti veness of vari ous
additives ,the fabric we ight gai n was onl y 1.4% . With acid catalysts is as follows:
active hydrogen compounds (a lcoh o ls , phenols, Succinic < lactic < malic < glycolic < citric < taJtaric acid .
amides or thiol s) as co-reactant, much higher fabric The extent to which a straight-chain g lycol
weight ga in could be obtain ed . But probl e m with increased DP performance depended primarily on th e
MgCI 2 is that it prod uces fabric yellowing an d severe molecular chain le ngth of the g lycol. The optimum
fabric stre ngth loss. Th e use of aluminium sulphate as le ngth was approximately six atoms, exc luding the
the curing catalyst leads to the hi gh levels of wrinkle terminal hydroxyl groups. The role of the glycol is as
resi stance. Excess of g lyoxa l appears to serve as a 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 125°C (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 (170°C) 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- 160°C 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 separately or in suitable combinations, employ ing
acids studied with respect to the level of DP pad-dry-cure techniqu e. Treatment with 10% acrylic
performance, speed of curing, laundering durability, ac id at 30°C and pH 7 produced optimum effects; a
retenti on of fabric wh iteness and free from odour. batching time of 45-60 min at 30°C followed by
Recently , malic acid activated by BTCA or small drying of th e batched fabric at 95°C for 5 min and
amounts of BTCA with hi gh concentrations of citric cu ring of the dried fabric at 140°C for 5 min produced
ac id as a DP finishing agent have also been found to jute fabrics with 238 ° (W+F) wrinkl e recovery and 2.6
be very effecti ve. cm bending length while untreated jute fabri c had
Saraf 17 has reported th e use of two commercial 143° (W+F) wrink le recovery and 3.8 cm bending
non-formaldehyde crosslinking agents, Natrium- NFO length. Na3P04 catalyst allowed es terificati on of AA
and Natrium-CRA , for cotton and polyester/cotton wi th cellulosic, hemicellulos ic and li gnin constituents
blends. At 15 % Natrium-CRA bath concentration, the of jute, and K2S20 S catalyst faci litated radical
wrinkl e recovery angle of cotton was found to be polymerization of acrylic acid, leading to some degree
240°C when cured at 170°C for 1 min. of crosslinking of the po lymer chain of jute.
fabric was padded twice with 100giL EPTA aqueous these deficiencies , adding value to a wrinkle - free
solution, dried at 40°C and then treated with 8 giL garment. One function of a softener is to modify the
a2C03 at 75 °C for IS min . The wet crease recovery hand or feel of a fabric to reach the desired effect. The
angle was improved from 200° (untreated) to 282° softener must also lubricate the fibres to increase
after finishing. The breaking strength of finished silk abrasion resistance and tear strength. The softener
increased by more than 10% and the whiteness also functions as a sewing lubricant, as high needle
decreased by about 2 .8%. Finished silk fabrics have speeds can generate enough heat to melt and fu se
good laundering durability; after 20 cycles of home synthetic fibres. Sewing damage, such as broken or
laundering,the wet resiliency retained was 95 % of that fused yarns, causes garments to be rejected by the
of the unwashed fabrics durability. customer.
Shiozaki and Tanaka 29 have analyzed the reactivity There are four basic classes of softeners, viz.
of epoxide onto silk and demonstrated that the anionic, cationic, non-ionic and blended systems. The
modifications with epoxide onto silk improve general characteristics of these softeners are discussed
moisture absorption, chemical resistance, and wash below in greater detail.
and wear properties . The four epoxides used were
glycidol, ethylene glycol diglycidyl ether, tolyl 3.1 Anionic Softeners
glycidyl ether and resorcinol diglycidyl ether. From The anionic softeners are generally sulphated or
the amino acid analysis of the silk treated with sulphonated compounds used primarily to lubricate
epoxides, it may be concluded that the epoxides react yarns or fibres through processing. Generally, the
with the side chains of the silk fibroin , such as lysine, anionic softeners are good lubricants, provide soft
hi stidine, arginine and tyrosine, thereby suggesting handle and show good stability to alkaline conditions.
that most of the weight gain due to the fibre treatment Most of them show good heat stability and some have
is distributed uniformly throughout the cross-section good yellowing resistance.
and does not occur near the fibre surface. They also However, anionics tend to provide inferior softness
reported that epoxides form crosslinks between the compared to the cationics and non-ionics.
adjacent silk fibroin molecules and the hydrogen Furthermore, they have limited durability to
I
bonds between the hydroxyl groups of epoxide laundering or dry cleaning. The major limitation
molecules attached to the side chains of the silk comes from their negative charge, which causes
fibroin 'o. incompatibility in resin finishing baths and makes
Chemical mod ification of silk fibres by graft them most sensitive to water hardness and
copolymerization of vinyl monomers and by reaction electrol ytes.
of epoxides and dibasic acid anhydrides, for example
phthalic, succinic and glutaric anhydride, have also 3.2 Cationic Softeners
may occur with oleic or tallow fatty acid types. To textile applications are generally in the range of
achieve maximum lubricity and strength properties, 10,000-12,500 centistoke. Polydimethylsiloxanes
many formulations are made with a significant portion impart desirable properties to fabrics due to their
being polyethylene. Typically, a blend will contain 2 flexible polymer backbone, stable bonds and low
parts polyethylene lubricant to I part aminoamide or intermolecular forces. However, the softening effect
imidazoline. Cationic softeners, as a result of their is not very durable to washing since there are no
positive charge, will be attracted to a cotton or reactive sites in the polydimethylsiloxane polymer.
synthetic fabric and can be readily exhausted from a
long bath or a dyebath. They tend to be compatible 3.4.2 Reactive Silicones
with most resin finishes. However, the cationic These are polydimethylsiloxane polymers modified
softeners have a tendency to change the shade or with silane hydrogen or silanol functional groups.
affect the fastness of certain dyestuffs. The Two mixed polyorganosiloxanes are also made, e.g.
development of a fishy odour on a fabric can be poly(methyl hydrogen siloxane). Conventional
another problem with certain systems. reactive silicones form a crosslinked siloxane network
on the fabric surface in the presence of water and an
3.3 Non-ionic Softeners organometallic catalyst. The crosslinked polymers
Non-ionics are the most widely used softeners provide durable softeners better than POMS. Silanol
which include polyethylenes, glycerides such as functional polymers are also the basis for silicone
glycerol monostearate, ethoxylates such as elastomers and textile finishes to improve hand and
ethoxylated castor wax, coconut oil, corn oil, and performance of durable press fabrics .
ethoxylated fatty alcohols and acids. The non-ionic
softeners offer excellent compatibility in resin baths 3.4.3 Organo-functional Silicones
and are easy to mix into a formulation. They generally Aminofunctional groups which are bound to
have little or no effect on the shade of dyed fabrics. polydimethylsiloxane backbone improve the orientation
Most are resistant to discoloration and yellowing.
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
and substantivity of the sili con on the fibre . The modified silicone softeners. This chemical modificati on
improved ori entation of aminofunctional silicones res ults in the formation of a stable emulsion of amide
leads to an extremely soft hand, which is frequ entl y modified silicone with non-yellowing attributes and a
described as 'Supersoft ' . In thi s, organo-reactive distinguishable change in softening properties. In
groups such as amines, epox ides and alcohols are addition, aminosilicone emulsion modified with T A-
introduced in the PDMS . 15 exhibits film forming and elastomeric properti es .
New Amino FUllctiollal Silicones: Amino gro up A new product Magnasoft SRS , which is a blend of
(primary to terti ary) in polydimethylsiloxanes was Magnasoft Plus (amino-silicone) and polydimethyl-
substituted. The structure of the amino group In siloxane-amino polyalkylene oxide block copolymer,
PDMS is as und er: provides good softness along with soil release on
polyester/cotton blends . Magnasoft HSSD with both
Amino Abbreviation R
pendant alkyl amine and polyether based polydi-
Primary -NH2 methylsiloxane terpolymer has been evaluated as a
Secondary NH-methyl -NH-Me softener for soi l release on wri nkle-free garments in
NH-butyl -NH-(CH2hMe conjunction with fluorocarbon soi l release agents.
NH-Iauryl -NH-(C H2)I IMe Softeners for terry towels available in the market
NH-cyclohexyl -NH-C 6 HII are classified on the basis of their durability as
Terti ary -NEt2 permanent hydrophilic and semi-durable hydrophli c.
On com paring the effects due to pnmary, Permanent hydrophilic: These softeners are usuall y
secondary and tertiary am ines, it is ev ident that organo-modified silicones. These products offer an
wh iteness, water absorbency and soi l release improve excellent handle along with hydrophili ci ty, which can
with the increasing degree of substitution from last for the lifetime of the fabric (15-20 washes).
primary to secondary to tertiary. Semi-durable hydrophilic: Softeners classified
Improved whiteness arises from the chemical under this category are normall y a combination of
structure of the am ino functional groups. The th ermal silicone and cationic components. Towels finish ed
yellowing is du e to oxidati ve decomposition of the with such softeners sometimes specify that it will
am ino group, form ing chromophoric groups. The show improved hydrophilicity after one wash. These
degree of imp rovement in whiteness on changing softeners offer an adequ ate-to-excellent hand le and
from primary to tertiary amino groups parallels the low hydrophi licity.
slowing of thermal degradation, as the number of Resi l Chemicals42 have introduced a range of
alkyl substituents increases. Only the si licones si licone products, for example RESIL Hydra range is
substituted with secondary ami nes show values as a new generation of softeners catering to the special
good as the si licones based on the amino ethyl and requirements of a terry towel finish -excellent
am inopropyl groups which have been commonly used hydrophilicity, soft fluffy handle, durability and non-
so far. An optimal combi nation of treatment effects yellowing-leaving the towels look fresh wash after
can be obtained with secondary am inofunctional wash.
silicones. All silicones substi tuted wi th secondary Silicones have also been used to improve the all-
ami nes, except for the NH-butyl si licone, produce a rou nd properties of si lk fabrics 43 . Table 3 shows the
soft hand th at is simi lar to that produced by the usual results of the crease recovery properti es of si licone
NH-ethylene ami ne modified silicone. NH-ethylene fin ished fabrics . It is observed that the recovery angle
amine substituted si licones have a relatively strong is hi gh in amino silicone compared to fatty amide,
water repellent effect. This effect is lower for polysiloxanes and si licone softeners. The improved
si licones substituted with secondary amines . recovery angle is because amino silicones are
Di fferences in soil release properties are minimal crosslinked with the fibre. The recovery properti es of
between th e si licones with secondary amine the silicone finished fabrics after washing does not
substi tuents. show any marked diffe rence in the recovery angle.
Czech et 01.41 demonstrated the effect of Shenai 44 used non-ionic surfactants with
"Magnasoft TA-\5" add iti ve (which is based on considerable water solubility made from the mixed
dialkyl oxalate) on ye ll owing properties of amino type of poly(orga no-s iloxanes). A very useful
170 INDI AN J. FIBRE T EXT. RES., MARCH -JUNE 200 1
o Cotto n kni t
.c
0, 18 rza Visc os e rayon
.0
• Alkali stabl e (pH 9-10) ~ 6
Enzymatic hydrolysis to improve wetti ng and concentrations (1.05, 5.3 1 and 16.04 %). Enzyme-
absorbency of polyester fabrics has also been reported treated fabrics showed minimal fibril lation compared
by Hsieh and Cram 58 . Six hydrolyzing enzymes to th ose submitted to simulated laundering condition s
(Table 4) to improve th e hydrophilicity of several without enzymes. Neither enzyme concentration nor
polyester fabrics were used. Five of the six lipases agitation affected the low-stress mechanical properti es
improve the water wetting and absorbent properties of but did influence the tensile properties. The 10weSl
enzyme concentration was less detrimental to the
reg ular polyester fabrics more than the alkaline
tensile properties, whil e inhibiting fibri llati on.
hydrolysis under optimal conditions (3N NaOH at
Production trials and monitoring in garment
55 °C for 2 h). Compared to aqueous hydrolysis, the process ll1g fac iliti es have show n that fabric
enzyme reacti ons are highly effective under more breakdown is significantly reduced when engi neered
moderate conditions, including a relatively low component cel lulases are used as compared to
concentration (0.0 I giL), a shorter reaction time (10 conventional who le cellulases. This is particularl y
min ), ambient temperature of 25 °C and no buffer. evident on delicate fabric s and lyocell blends. Process
Improved water wettabi lity is accompanied by full conditions used were : liquor ratio of 10: 1, pH 5.0,
strength retention compared to the significantly treatment temperature of 58°C and treatment time of
reduccd strength and mass due to alkaline hydrolysis. 45-60 min. Th e enzyme dosages were adjusted to
Interestingly, the wetting and absorbent properties of achieve a hi gh degree of defibrill ation . On 100%
sulphonated polyester and microdenier polyester Iyocell, the handle attributes of the engineered
fab rics are also improved by lipase. component cellulases treatments were assessed high er
than that of the whole cellulase, but the differences
·U Finishing of Lyocell 5%1 were smal l at the dosages tested. Much clearer
A concern encountered with use of Iyocell fibre s differences were seen in the lyocell/cotton and
has been th e fibrillation of fibre surfaces under Iyoce ll/linen blends 60 . The panelists consistently rated
mechanical stress or when swollen with water. They treatments by engineered component cellulases as
have a tendency to fibrillate because of th e hi gh softer and bulkier compared to the whole cellulase,
orientation and lack of lateral cohes ion. If con troll ed, irrespective of the dosages. This suggests that hand
this fibrillation can provide a soft finish for Iyocell preference may be directly related to the composition
fabrics, but under continued laundering the fibrillation of the enzymes and not to the enzyme dosage. These
wil l become worse and may adversely affect th e three enzyme compositions influenced th e fabric hand
appearance and hand of a textiIe material. Fibre properties differently due to the possible differences
processing parameters can, therefore, be adapted to in their mode of action 61 .
minimize the fibrillation problem in the spun fibres.
Fibre-reactive dyes, crosslinking resins and enzymc 5 Plasma Treatment62-~
treatments have been investigated as methods for The application of the plasma treatment has been
reducing the degree of fibrillation in Iyocell fabrics. demonstrated for the surface modification of various
In one of the process, the fabric samples were textiles. A lot of envi ronmental and production
enzy me treated with a commercial whole cellul ase in problems can be solved by using a non-equilibrium
a Launder-O-meter machine at 50°C for 60 min , both low-temperature plasma. The pl as ma processes are
with and without steel balls for agitation. The liquor- dry ones and do not require wate r or non-aqueous
to- fabric ratio was 20: 1 and an acetate buffer was soluti on. Promising applications of gas discharge
used to maintain the pH at 4.8 . A buffer control with plasma for the activat ion of chemical reactions in
no enzyme was run in addition to three enzyme liquids have also been reported .
58
Table 4 - Varieties of lipases used in improv ing th e wettabilily of polyesler fibres
Lipase Supplier or manufaclU rer Source Form ACl ivity Purily
A ICN Hog pancreas Powder 30.8 units/mg 2.8% mo isture. 0.9% fat
13 ICN Porc ine pancreas Powder 16 ul1its/mg Diastase- free 12'K protein
C Sigma Wheat ge rm Powder 7.6 units/Illg 95 % protein
0 Sigma Candida mgosa Powder 250,000 units/mg 95 % protcin
E Genencor Inlenwli on<J1 Pselldol/IO/ws lIIe//{/ocii/(/ Liquid 250.000 units >90%
F Novo Nordi sk Aspergilllls ory~ae Liquid 100,000 units >90%
BAJAJ: ECOFRIENDL Y FINISH ES FOR TEXTILES 173
The plasma techniqu e is based o n ionised gases cross linking, biocompatibility, protection and anti-
64 67
produced by electri cal di scharges. In fact, the wear, and chemical affinity or inertness - . Relative
coupling of electromagnetic power into a process gas free-radical intensity of th e plasma-treated fibre s,
generates the plasma medium comprising a dynamic measured by ESR , increases in the following orde r:
mi xture of ions, electron s, ne utron s, protons, free
Cotton> Wool> Silk> Nyl on 6 == PET.
radicals and metastabl e exci ted spec ies which enable
a variety of surface processes, e.g. surface activation The natural fibres, espec iall y cotton and linen,
for creati ng reactive etching, dissociation of surface showed larger free-radical intensity th an the
contam inants (scouring/bl eachin g) and deposition of regenerated cellu lose and synthetic fibres .
coatings for specific applicati ons. In all , the p lasma The ill-situ plasma polymeri zati on for grafting of
treatment is a hi ghly surface speci fic of th e material polymers on to the textile surface has also received
« 1000 A) which does not affec t th e bulk properties. co nsiderable attention for improving wettability.
The mean depth of plasma acti ve species action in Chemical grafting with various mo nomers onto
63 plasma-activated surface of cellulosics and other
po lymers is g iven in Table 5.
Depending on the gas pressure, two s ignificantly fibres has been reported for accomp li shing specific
different forms of discharges are known : properties.
U: Untreated reference
P: Plasma - treated
'"
Q.
E
CAC: Carnal-treated fabric
after application of the @ ®
'"
(/)
.S!
araldil-collagen resin
o 10 t5 20 25
Falling shrinkage , %
Table 7 - The f.\". f.\ w and DFE values and felted ball density of resistance even for very short plasma pretreatment
the fibres 72 times of 2 min. The extent of weight loss during
Sample/plasma f.\a f.\w DFE Felted ball density (D) washing is also minimized for all plasma-polyme r
% g/cm' applications relative to polymer-only or chlorinated-
Untreated 0.35 0. 16 37.3 0.064 polymer treated wool.
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%)" 5.2 Surface Modification of PET and Polypropylene Fibres
PM 0.51 0.32 23.4 0.019 (170.3 % )"
(Hydrogen/nitrogen.
Tsai et al. 75 have reported some encouraging
25 % :75 '70 ) results from the plasma surface treatment o f
"Values ill parentheses indicate % decrease in felted ball dens ity. polypropylene meltblown nonwovens in the UTK
one-atmosphere glow discharge plasma reactor. Thi s
values of the LTP-treated samples are much lower. reactor generates a large volume (up to 2.4 litres), low
The PN and PM treatments show the same decrease in power (less than 150 watts) , and uniform glow
D values, which is better than the PO treatment. These discharge plasma in a parallel plate configuration with
changes are th e same as observed in DFE results, oval electrodes of 23 I cm 2 face area, the lower
which confirm that th e DFE and the ball felting are electrode being covered with a 3.2 mm thi ck
related to each other. Based on the res ults of /..l values insulating Pyrex surface. The plates are set up in an
and DFE, it may be concluded that the nitrogen enclosed box that makes it possible to control th e
plasma and gas mixture plasma impart similar anti-
working gas used, and the spacing between the plates
felting effects to wool fibres and that their effects are
can be varied. This reactor is energized by a custom-
sl ightly better than the innuence of oxygen.
made high impedance kilohertz power supply capable
Ryu et al. 7 } used corona discharge for surface
of supplying up to 5 kilowatts of kilohertz power at
modification of wool fibres and fabrics. An electron
RMS voltages up to 10 kY, and over a frequenc y
spectroscopy for chemical analysis (ESCA) was done
range of 1-200 kHz.
to elucidate the changes in chemical composition on
the fibre surface. The corona discharge incorporates Tsai et al. 75 used two groups of working gases, CO 2
oxygen atoms into the fibre and increases wettability and CO 2 + O 2, to treat the webs of PP at different
and laundry-shrink resistance of wool fabrics, but the electrical and temperature conditions. Using CO 2
effects are smaller than those from low-temperature alone at a driving frequency less than 2 kHz would
oxygen plasma. It may thus be concluded that the not make the webs wettable, while using the mixture
plasma treatment is a good alternative to chlorination of CO 2 + O 2 as working gas could make the webs
pretreatment in Hercosett process of shrinkproofing of wettable if treated at low temperature for I min (Table 8).
wool. Shisho0 76 and Sarmadi et ol.77also reported the
The effect of glow-discharge polymer treatments increase in surface energy for PP and PET samples
on the shrinkage behaviour and physical properties of after plasma treatment, confirming the presence of
wool fabric has been studied by Zuchairah et 01.74. In polar groups on the polymer surface and thereby
this work, four different polymer sys tems, viz. decreasing the contact angle. Such low- temperature,
BasolanSW (cationic polyether in isopropanol low-pressure plasma treatment is effective in inducing
so lution, BASF), Basolan MW (weakly cationic polarity at th e surface vis-a-vis hydrophillic surface
aminofunctional polysiloxane microemuls ion , BASF), layer. Thus, it can reduce the high consumption of
Polymer G (cationic amide-type res in in aqueous chemical wetting agents normally required III
solution plus polyethylene wax emulsion as softe ner) , chemical processing of textiles.
and Polymer PL (cationic acrylic copolymer in Grafting of PP fabrics under AN-RF plasma was
aqueous solution, ICI Stelco), are applied onto carried out using ground pressure of 0.05 mm Hg , 0 .3
plasma-treated wool fabric to enhance the degree of mm Hg pressure in the reactor and 60W and 100W
shrink resistance. The leve l of shrink resistance varies RF power. Reaction time was varied between 30 sand
sign ificantly with plasma polymer treatments, 5 min77 .In polypropylene, the plasma is generated by
depending on th e kind of polymer sys te ms applied, inductive coupling in a tubular shaped argon container
with Polymers PL and G conferring excellent shrink and needle valve system permitted acrylonitrile (AN)
176 IN DIAN J. FIJ3R E T EXT. RES., MARC H-J UNE 200 1
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
to now into the reacti on vessel. The va pour press ure prcdomi nate und er certain ex peri men tal conditions.
of the AN is above the operati onal reactor press ure Others have also reported that ammoni a plasmas do
and co nsequcntl y th e monomer is easi ly fed in gas not produce primary amin e effi cie ntl y, and
form to the reacti on chamber under vac uum . consequ entl y saturated and un saturated amin es have
PAN surface graft ed PP fabri cs ex hibited imp roved bee n proposed in order to create reactive surface
water absorpti on and dyein g properti es du e to th e amin e groups.
presence of nitrogen and carbon based un saturated
linkages and formati on of seco nd ge nerati on -C=O 5.3 Water Repellency and Surface Dyeing of Polyester Fabrics
groups. Effici ent graftin g takes place eve n in short Po lyes ter fa bri cs 7,) have also bee n successfull y
treatment times. tre ated with O 2 or CF4 plasma under di ffe rent power,
Reactive amin e group implantati on on polymer press ure and time co nditi ons. Elec tro n spectrosco py
surface by cold pl as ma reacti ons also represe nts one for chemical analys is (ESCA) clearly indicated th e
of th e possibilities for surface fun cti onal iza ti on. One surface ox idati on and nuoridati on. Oxyge n plas ma
approach for att ac hing reac ti ve amin e groups is to use trealment im proved both water upta ke and sur face
ammoni a plas ma. Ca rba ugh cf a/.78 have studi ed th e dyeabi lit y, 'v" hil e CF~ plas ma trea tme nt improved
pl as ma decompos iti on of ammonia and ha ve proposed wal eI' repellency along with im proved surface
th e foll ow ing mec hanis m: dyeabi lit y with c. 1. Bas ic Blue 3.
Unex pec ted su rface dyeabilit y with a basic dye and
NH1--+ NI-i' + H ... ( I )
wat er repell ency effee ts ont o CF4 plasma trea ted PET
H + NI-I,1- -+ NH z + 11 2 ... . (2)
fabric s have bee n related to inlense nu ori da ti on
11 2 --+ 2 I-I (3)
leadin g to tenon-l ike surface and simult aneo us
2 NI-I 2--+ :NH + NH1 (4)
un sa turat ed bonds and trapped free radi cal s. The
2 NI-I 2--+ N2H4 (5)
mechani sm of th e reacti ons fo r two ty pes of gases, O 2
2: NH--+ N2+H 2 (6)
and CF~, in th e discharge sys tem is as foll ows:
It is sugges ted th at the primary amin e radi cal s are In O 2, a mi xture of ac ti ve oxyge n spec ies is
most likely th e entit ies to do min ate th e reac ti on produ ced in th e discharge cham ber. Some of the
mec hani sms and co mbine with surface radi ca ls. reacti ons whi ch are beli eved to occur are:
Howeve r, because of th e coex istence of a signifi cant
!l umber of mo no- and multi -rad ical spec ies and O 2--+0+ 0 (7)
va ri ous reacti on poss ibilities in th e plasma stat e, th e 0+0--+ 0 2 (8)
molecul ar frag ments other tha n NI1 2 can al so 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
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
O~ . /'O
was hes
N 2.50 30 2.83 > 5111111 Kill all
I 4.65 30 1.42 > 2111 111 >3 111 III
H Hyda ntoin rings
2.47 5 2.88 > 1 III III Kill all
Fig. II -Reaclion of MDMH (lllonolllethylol-5,Y - 4.56 5 1.64 >2 III III >3111111
di lllethylhyda ntoin ) wit h ce llulose (ref. 98)
" Biosil" and "Episcall " finishes have recei ved
the treated fabric is attributed to the reversible acceptance not o nly for underwear and foundati ons
ox idati ve properti es of cyclic hal a min e stru ctures. Th e worn in direct co ntact with the skin , but also
effectiveness of th e antimi cro bi a l fabrics is re lated to freq ue ntly in th e sec tor of work wear and sportswear
the amo unt of active hal a min e agents in corpo rated
w ith th e ir hi g h occ urre nce of sweating. Bacteria-
o nto the fabric s . resistant/deodorizing fini shes such as " Bi os il" and
The bi oc idal functions on the fabrics are achieved " Episcall" have beco me indi spe ns ibl e for socks and
by two ste ps of c hem ica l process in g including panty hose as we ll.
fin ishing under acidic co nditi o ns a nd rinsing with
In addition to after-fini shin g, there are other
chlorine bleach . Each of th e processes may have its
products with knead-in bacteri a- resistant agents fo r
ow n impact on physical properties of the fabric .
syn thetic fibre, which can bring about similar effects.
Chemical fini shin g of the hydanto in compound o nto
T oyobo has developed and commerciali zed
ce llulose was perfo rmed unde r acidic conditions that " Feelfresh" (acrylic fibre) and "B ioguard-N " (nylon
are quite harmful to the chem ica l structure of cotton fi la ment) .
ce llul ose. Active chl ori ne in bleaching so luti o ns
Kanebo loo launched an antibacterial nylon fire
usuall y damages th e te nsil e stren gth of fabrics due to " Li vefresh-N ". Thi s fibre is the first o ne made w ith an
its ox idative pro pe rti es. T hese fac tors, affecting th e ino rganic antibacte rial additive Ag-zeolite kneaded in .
mechanical properti es of the treated fabrics , should be " Livefresh-N " is used in the fi e ld of innerwears
investigated to e nsure the appropriate properti es of the
including lingeri es and hos iery . But there were
antimicrobial fabrics. Bioc idal prope rti es o f cotton
pro blems such as yarn breaks in di fferent processes
fabrics processed under different pH are g iven in and yellowing when exposed to heat a nd li ght.
Table 13.
Especially, nylon polymer has a re markabl e yellowin g
Biosil 9<J fini sh e mpl oys an agent which joins compared with other po lyme rs. In stead of Ag-
quaternary ammonium salt with organosilicone . By zeo lite 'O' , it has slow re lease g lass phosphate wi th
graft-poly merizin g with fibre, thi s o rganos ilicone is silver ions as an a ntimicrobial additive kneaded into
affixed to fibre firmly. For thi s reason, the agent does fibres. This enabled to maintain antibacterial effect
not leach out even by washing. Th e quaternary with less amount of additive. At the same time,
ammonium salt destroys cell membranes o f bacteri a. yellowing defect was improved by far.
Bi os il is also characterized by the fact that there is no
harmful influence res ultin g from the oozing of the 6.1 Bacteria-Resistant Finishes: Escola and Epicomodo
agent. [n princ ipl e, "Episca ll" a lso employs In contrast to bacteria-res istant/deodorizi ng
qu aternary ammonium sa lt as a base. Toyobo has finishes, which reduce th e g row th of bacteria to
deve loped " Epi scall " as a genera l purpose type of prevent the generation of odors, bac teri a-resistan t
" Biosil". "Epi sca ll " can be treated to any fibre, as is finish gives more priority to the e ffect of prev entin g
th e case with " Biosi l" . T oyobo has ado pted "Biosil", g rowth of germ s.
however. mainl y for cotton tex til es, while " Episcall" For so me time, the attention has been focussed on
is for all tex tiles. The employed agent, nam ely " Dow Methicillin-resistant Staphilococcus aI/reus
Corning 5700" (s ilico ne quaternary ammonium salt), (MRSA)I02. Abu ses of antibiotics have produced a
sati sfies stri ct criteria issued by th e U.S. Environment mi serabl e si tuati o n in which a ntibi ot ic-resistant
Pro tecti o n Agency (EPA) and a g uarantee is g ive n to mi crobes have grow n conversely and there is no way
its safety as we ll. 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 clothi ng may cause discomfort. Thi s problem arises
responsive actions have been progressing against because of the water-vapour impermeability of the
MRSA . Moreover, actions were requested even for polymer coating.
clothing such as uniforms and interior goods such as To overcome this problem, breathable polymer
curtains to prevent the transmission of germs, along coatings are now available th at have made possible
with the steri li zation of everything which is used at great improvements in the comfort of this type of
hospitals, in order to prevent hospital infection . clothing.
"Epicomodo" is a fabric which Toyob0 99 has
7.1 What is a Breathable Fabric ?
developed to cope with MRSA, since it has become a
A breathable fabric is waterproof and breathable
serioius task to keep a clean in-hospital environment.
because of the enormous size difference between a
Toyobo has proposed 100% polyester, polyester/
water droplet and a water vapo ur molecule 1ol . The
cotton blends and other fibres in a number of
former is 100 J..lm in diameter whereas the latter is
combinations for curtains, white coats and bedding
0.0004 J..lm, i.e. there is a factor of around 2,50,000
used in hospitals. The mechnism of bacterial-resistant
between the two sizes. Microporous
fini sh used for Epicomodo is as under:
polytetrafluoroethylene (PTFE) Gore-lex laminates
The agents with positi ve ions attract germs to their
have been successfully introduced as breathable
environment by acting upon their cell membranes
fabrics. Comparative assessment of Gore-tex and
with negative ions to control the activity of the germs
Neoprene vapour barriers in fire fighter sui ts has also
by destroying cell membranes as shown in Fig. 12.
been made.
One bath process for dyeing and simultaneous
antimicrobial finish by methanolic extract (1-5 %) of 7.2 Classification of Breathable Fabrics
Tulsi leaves (OCillllllll sallctulII) on cotton l03 has been The breathable fabrics can be classified into three
investigated. It is believed that urosolic acid main categories:
(C30H4s0 3) is the active ingredient which inhibits the
growth of several strains of Staphylococci. 7.2.1 High-density Woven Fabrics
High-density wovens owe their breathability to the
7 Waterproof Breathable Fabrics HJ.I.I12 densely woven, thin and smooth yarns that are usuall y
Waterproof/moisture permeable fabrics from made from microfibres. This type of weaving results
several sy nthetic fibres have been designed for in a windproof fabric with an excellent water vapor
skiwear, track suits, rainwear, and mountaineering permeability compared with laminates and coatings.
clothing. Its water impermeability is, however, not very high ,
Light weight fabrics coated with poly(vinyl even though a water-repellent finish is usuall y
chloride), polyurethane and other sy nthetic rubbers applied. The major advantage of these fabrics is their
have become increasingly popular for foul-weather good grip. For those applications where grip, water
clothing. Although garme nts manufactured from these vapour permeability and windproofing are more
fabrics provide excepti onal protection against rain important than water impermeability, marvellous and
and, to a less extent, wind penetration, but fashionable clothing can be made from these fabrics;
considerable build-up of moisture vapour inside the they can be found in ski clothing.
1
1\!icrobial ........
conlrolling_ _ _ _ _...-.!~__..._I1I....-II~- controlli
ag~ nt agent
Fibre
Fig. 12-Bacterial -resistant mec hani sm of £picolI/odo (ref. 99)
BAJAJ: ECOFRIENDLY FINISHES FOR TEXTILES 183
structure which has to be crushed . Breathability is matrix of th e fabric , determine the overall water
good but water-proofness has to be improved. An vapour transport rate through the layered fabrics.
example is Dicryl an system of Prersree/Ciba Geigy . The overall water vapour and heat transport
Performance of various breathable fabrics is shown in characteristics of a fabric should depend on oth er
Table 14. factors such as the water vapour absorbability of th e
7.3 Evaluation of Breathable Materials
fibres and the porosity, density and thickn ess of th e
The two most important characteristics of fabric. The overall dissipation rate of water va pour
breathable fabrics are water vapor and heat transport. depends on both the vapour tran sport rate and the
In order to gain an insight into the transient states of vapour absorption by fibres, which are mutually inter-
such transport across a set of layers of fabrics, an MU related . Water vapour transport is governed by th e
water vapor transport simulator (MU- WYT simul ator) vapour press ure gradi ent that develops across a fabri c
has been developed. layer. When a fabric is subj ected to given
It ha<; been demonstrated that the water transport is not environmental conditions, th e ac tual water vapour
in flu enced significantly by sUlface charactelistics- transport rate greatly differs depend ing on th e nature
the hydrophilic or hydrophobi c nature of fabrics. On of th e fibres , even when oth er parameters such as
the other hand, when liquid water contacts a fabric , density, porosity and thickn ess are nearly iden ti cal.
such as in the case of sweating, the surface wettability To understand thi s process more cl earl y, Robin
of fa bric plays a dominant role in determining th e Howie from the Institute of Occupat ional Medi cine in
water vapor transport rate th rough layered fabrics. In Edinburgh has developed a meth od for calcul atin g the
such a case, the wicking characteristi cs, which requirements that a breathable clothing should have
determin e how quickly and how widely liquid water under specific conditions, by takin g the foll ow ing
spreads out laterally on the surface of/or within th e parameters into acco unt 11 0 :
lll9
Table 14 - Brea thability determin ed from a co mparati ve wea rer tri al
-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
References
en "- u 0
I Holme I, Tex , Horizons, 17 ( 1997) 17.
0 1000
-I 2 Anon, Inr Dyer, February ( 1998) 25 .
iii
~-0'----eo-----.,oo- 3 Blanch R M, Me/liand 1/1', 2 ( 1997) 94.
~ 4 Hickman W S, J Soc Dye rs Colollr, 109 ( I) (1993) 32.
0 5 Vukusic S B, Solj acic I & Katovic D, Alii Dyes' Rep, 87 (5)
- 20 o 20 40
( 1996) 20.
Temperature , 0 C 6 Harper R J & Frick J G (11'), Alii Dyes' Rep, 70(9) ( 198 1) 46.
7 Welch C M, Tex , Chelll C% r, 16 ( 12) (1984) 265 ; Tex, Res
Fig. 13 - Temperature-dependence of water vapour diffu sion J, 53 (3) ( 1983) 18 1.
resistance for four membrane type materials (two hygroscop ic, 8 Welch C M & Peters J G, Tex , Res J, 57 (6) ( 1987) 35 I.
two non-hygroscopic) (ref. 11 2) 9 Blanchard E J & Reinhardt C M. Alii Dyes' Rep. 78 (2)
( 1989) 30.
• Th e heat to be carried off by cl othing (as a function 10 Rafai R. Abdel-Hafiz SA & Hebeish A. Alii Dyes' Rep, 8 1
of physical exerti o n). (4) (1992) 42.
• The estimated the rmal resistance of clothing II Welch C M, Tex, Cho n C%r, 22 (5) ( 1990) 13.
(therm al conducti vity). 12 Welch C M & Andrews B A K, Tex, Ch elll Co /nr. 21 (2)
( 1989) 13 .
• The relative amb ien t humidity.
t3 Welch C M, Alii Dyes' Rep, 83 (9) ( 1994) 19 .
• Th e ambi e nt ai r velocity. 14 Welch C M & Peters J G, Tex, Chelll C%r, 25 ( 10) (1993 )
On the bas is of thi s model, the req uired values for 25; 29 (3) (1997) 22 .
air and water vapour permeabi lity are ca lc ulated for IS Welch C M, Tex, Chelll C% r, 29 (2)( 1997) 2 I.
vario us degrees of physical exerti on under differe nt 16 YangCQ, Tex,Res J ,63 ( 12) (1993)706.
17 Saraf N M, Alii Dyes' Rep,83 (8) ( 1994) 47.
ambient temperatures. 18 Mos tafa Kh . M, Alii Dye.1f Rep, 85 (9) ( 1996) 85.
For a surgeon in an operatin g room, the values are 19 Mostafa Kh M, EI-Sanabary A A & Youssef M A. Alii
given in Tab le IS .1t is interesting to note that the Dyes' Rep, 86 (6) ( 1997) 30.
surgeon who is working at 20DC at a mode rate work 20 Ghosh P & Das D, E liI' PO/YIII J , 36 (2000) 2 147.
21 Ghosh P & Das D. J App/ PO/YIII Sci, 68 ( 1998) 63.
pace, would feel co mfortabl e, provided the air
22 Kawahara Y, Sh ioya M & Takaku A. Alii Dyes' Rep, 83
permeability is 100 IIm2/min and the water vapour ( 10) ( 1994) 28.
permeability 400 g/m2/24h. Hi s cl othin g may the n be 23 Kawahara Y, Shioya M & Takaku A, Alii Dyes' Rep, 84 (4)
call ed breathable. ( 1995) 36.
24 Tsang B & Dhingra R C, Tex , Asia. 27 (5) ( 1996) 56.
Gibson 11 2 has described the various tes t method s 25 Yang Y & Li S, J Text 1/1.1"" 84 (4) ( 1993) 638 .
for studyi ng the water vapour transport and gas fl ow 26 Yang Y & Li S. Tex, Chelll C%r, 26 (5) ( 1994) 25.
properti es of tex til es, polymer me mbran es and fabric 27 Yang Y & Li S, Alii Dyes' Rep, 83 (2) (1994) 27.
lamin ates. In thi s context, Dynami c Mo isture 28 Cheng H & Kai S. Alii Dyes' Rep, 87 (3) ( 1998) 42.
29 Shiozaki H & Tanaka Y, Die Makromol C/W/I , 143 ( 1971 )
Permeation Cell (DMPC) method sati sfies the need
25.
fo r quick automated me thod for th e mass transport 30 Tsukada M & Shiozak i 1-1 , J App/ PolYIII Sci. 37 ( 19R9)
properties. DMPC method is ideally suited for 2637.
temperature-dependent di ffusion and concentration- 31 Tsukada M, Nagura M, Ishikawa 1-1 & Shiozaki 1-1 , J ApI'/
dependent diffu sion in membrane la min ates. An PO/YIII Sci, 43 (199 1) 643 .
32 Tsukada M, Shiozaki H & Freddi G, Mellio/ld Texli/ber,
exa mpl e of th e temperature-dependent water vapour August( I 993) 778/E287 .
di ffusion behaviour of four me mbran e based materials 33 Teli M D. Paul R & Pardeshi P D. CO/ai/rage , June (2000)
is shown in Fig. 13 . Res ults are show n for the mean 17.
relative humidity condition of 0.40 (40% ) (average of 34 Nostadt K & Zyschka R, Colol/rage. January ( 1997) 53.
0.80 on one side and 0.0 o n th e oth er). Res ults for 35 Carn eiro A, Marimba A, Souto A p. Dias S & Azevedo M,
Tex , Asia, June (2000) 3 1.
other mean relative humidity conditions showed that 36 Tel i M D, Munawa r Q. Chaudhari S & Saraf N. In' Dyer.
the te mperature effects on the measured diffusion Ap ril (2000) 25 .
resistance are much greater whe n the hydrophili c 37 Krefeld P 1-1, Me/liand Texli/lJer, 7 1 (1990) 699/E326.
186 INDIAN J. FIBRE TEXT. RES ., MARCH-JUNE 2001
38 Muller J, J Coated Fabrics, April (1993) 308. 75 Tsai P P, Wadsworth L C & Roth J R, Text Res J. 67 (5)
39 lang K 0 & Yeh K, Text Res J , 63 (1993) 557 . (1997) 359.
40 Boddeker B & Peters A, Int Text Bull (Dyeing/Printing/ 76 Shishoo R, J Coated Fabrics, July (1996) 26.
Finishing), January (1997) 13. 77 Sarrnadi A M . Ying T H & Denes F, Text Res J. 63 ( 12)
41 Czech A M, Pavlenyi J & Sabia A J, Text Chem Color, 29 (1993) 697.
(9) (1997) 26. 78 Carbaugh D .C , Munno F J & Marchello J M, J Ch em Phys,
42 Th e Resilient-Technical Re po rt,No. 3 (Res il Chemicals), 17 (1967) 5211.
2000. 79 Sannadi A M & Kwon YAH, Text Chem Color, 25 ( 12)
43 Yijaykumar H L & Muru ges h Babu K, Clothesline, (1993) 33.
FebruarylMarch (1995) 87. 80 Oktem T , Ayhan H, Seventekin N & Piskin E, J Soc Dyers
44 Shenai Y A, Text Dyer Primer, March ( 1994) 20. Colollr, 115 (9) (1999) 274.
45 Joyner M M, Am Dyest Rep, 77 (8) (1988) 36. 8 1 Jahagirdar C J & Yenkatakri shnan S , J Appl PolYIII Sci. 41
46 Spuy A Y, Int Dyer, October (1995) II. (1990) 117.
47 Cheng K P S & Wong C M, Text Asia, September (1998) 82 Akovali G & Takrouri F, J Appl PolYIII Sci, 42 ( 199 1) 2717.
55. 83 Wakida T , Cho S ,CIlOi S, Tokino S &. Lee M. TexI Res J.
48 Czech A M & Sabia A J, Am Dyest Rep,82 (9) (1993)58. 68 (I I) ( 1998) 848.
49 Karmakar S R, Colourage Anllual, (1998) 75. 84 Yohrer U, Asian Text J . Augu st ( 1998) 93.
50 Etters J N & Annis P A. Alii Dyest Rep. 87(5)( 1998) 18 ; 85 Seventekin N & Ucarci 0, J Text Insl. 84 (3) (1993) 304.
Colourage Anllual. (1998) 87. 86 Bohrindger A, Rupp J & Yonenaga A. 1111 TexI BIIII. (5)
51 Mehra R H. Mehra A R, Me hra Arun R & Shenai Y A. Text (2000) 12.
Trends. May (2000) 33 . 87 Refai R, Alii Dyest Rep, 81 (5) ( 1992) 40.
52 Almeida L & Cavaco- Paulo A, Mellialld Textilber. 74 88 Rajendran S, Ratnam T Y & Ramasamy S S , Asiatl TexI J.
(1993) 404/EI 84. November (1997) 29.
53 Chikkodi S Y, Text Chem Color, 28 (3) (1996) 28. 89 Yi go T L, Danna G F & Goynes W R. Text Chelll Colollr.
54 Kumar A, Yoon M Y & Purte ll C, Text Chem Color. 29 (4) 31 (I) (1999) 29 .
(1994) 37. 90 Payne J D & Kudne r D W, Alii Dyest Rep, 85 (5) ( 1996) 26.
55 Pant S & T aya l P, Illdian Text J, CX (4) (2000) 60. 91 Payne J D & Kudner D W, Text Chem Color, 28 (5) ( 1996)
56 Yoon N S & Lim Y J, Tahara M & Takagishi T. Text Res J, 28.
66 (5) (1996)329. 92 Cho J S & Cho G, Text Res J, 67 (12) ( 1997) 875.
57 Jova ncic P, Jocic D & Dumic J, J Text hlSt. 89 Pt. I (2) 93 Morri s E C, Yigo T L & We lc h C M . Text Res J. 51 ( 198 1)
(1998) 390. 90.
58 Hsie h Y L & Cram L A, Text Res J, 68 (5) (1998) 311 . 94 Points P S & Wad sworth L C , Text Chelll Color,18 ( I I)
59 Collier B J, Text Chelll Color & Am Dyest Rep, October (1986) 17.
(1999) 40. 95 Lee S, Cho J S & Cho G, Text Res J, 69 (2) (1999) 104.
60 Kumar A & Harnden A , Text Chem Color & Am Dyest Rep, 96 Kim Y H, Chok H M & Yoo n J H, TexI Res J, 68 (6) ( 1998)
September (1999) 37. 428.
61 Nikolov A, Int Dyer. July (2000) 30. 97 Chung Y S, Lee K K & Kim J W, Te ·t Res}. 68( 10) ( 1998)
62 Hollander A & Behnisch J, Asian Text J, August (1997) 49. 772.
63 Rybkin Y Y, Maximov A L, Gorberg B L & Titov Y A, 98 Sun G & Xu X, Text Chelll Color, 31 ( I) (1999) 21 ; 30 (6)
Asian Text J, October (1997) 30. (1998) 26.
64 Tomasino C , Cuomo J J, Smith C B & Oehrlein G , J Coated 99 Toyo bo. Jap Text News, May (1998) 78.
Fabrics. October (1995) 115. 100 Kawata T, Ch elllical Fibres lilt, 48 ( I) ( 1998) 38.
65 Jun g H Z, Ward T L & Benerito R R, Text Res J, 47 (3) 101 Stevenato R & Tedesco R ,Mall -Illade Fibre Yea r Book,
(1977) 217. 1999,30.
66 Bhat N Y & Benjamin Y N, Text Res J, 69 (I) (1999) 38. 102 T oray Industries, Jap Text News , Octo ber ( 1998) 76.
67 Sekar N, Colourage, June (2000) 39. 103 Ghorpade B, Tiwa ri Y, Mi shra A & Yankar P S, Asiall TexI
68 Hesse A, Thomas H & Hocker H, Text Res J, 65 (7) (1995) J, May (2000) 56.
371. 104 Schledjewski R, Schultze D & Imbac h K P, Asiall TexI J.
69 Wakida T , Tokino S, Niu S, Kawamura H, Sato Y, Lee M, June (1998) 36.
Uchiyama H & Inagaki H, Text Res J. 63 (8) (1993) 433. 105 Schledjews ki R, Schultze D & Imbach K P, J Coated
70 Kan C W, Chan K, Yuen C W M & Miao M H, Text Res J, Fabrics. 27, October (1997) 105.
69 (6) (1999) 407. 106 Kramar L, J Coated Fabrics. Octobe r (1998) 106.
71 Rakowski W, J Soc Dyers Colollr, 113 (9) (1997) 250. 107 Wadsworth L C & Allen H C (Jr), J Coated Fabrics. Jul y
72 Kan C W ,Chan K,Yuen C W M & Mi ao M H , Text Asia, (1998) 12.
October (1997) 39. 108 Pasq uale J A, J Coated Fabrics. Oc tobe r (1991) 77.
73 Ryu J, Wakida T & Takag ishi T. Text Res J, 61 (10) (1991) 109 Roey MY, J Coated Fabrics. July ( 1991) 20.
595. I 10 Kanneken s A, J Coated Fabrics, J uly (1994) 51.
74 Zuchairah I M, Pailthorpe M T & Dav id S K, Text Res J, 67 III Smith W C, J Coaled Fabrics. January (1986) 180.
(I) (1997) 69. 11 2 Gibson P W, J Coated Fabrics. April ( 1999) 300.