CHAPTER 19 63

SPECIAL CHEMICAL FINISHES

20.1 INTRODUCTION
This chapter deals with finishes of the cellulosic fabrics for certain specific
end uses like water-repellency, flame-retardancy and mildew and rot-
proofing. Such chemical treatments are mostly applied to the materials
required for commercial, industrial and military uses. However there are
notable exceptions to this generalised statement where these treatments are
used for apparel and household linen such as flame-retardancy of garments
and bed-wear for children and waterproofing of raincoats.

Like other finishes, the water-repellent and the flame-retardant finishes are
undergoing constant changes not only for improved results but also in
consideration of the ecological effects, ease in application and the last but
not the least, the ultimate cost. A relatively greater stress for improvement
has recently been on the fire-retardant finishes because these involve safety
of human lives. The old and the new finishes on these two subjects, both
temporary and permanent, are described below.
20.2 WATER- REPELLENCY AND WATER- PROOFING
In the past different terms were used to express the state of hydrophobicity
of a textile material and degree of effectiveness of a particular product.
Multiplicity of such terms was confusing especially when these were not
based on any precise and standard testing procedures. However with passage
of time all the hydrophobic treatments have been gradually classified into
two main groups termed as water-repellent and waterproofing finishes that
are expressed with fairly well defined characteristics. The term ‘water-
repellent’ expresses a degree of resistance of a fabric to surface wetting,
water penetration, water absorption or any combination of these properties
but its assessment is dependent upon the test conditions used. In general, the
water-repellent finishes are resistant to wetting and wicking by rain drops
but are permeable to air and also a little to the water vapours.

Waterproofing normally represents the condition where a textile material can

prevent absorption and penetration of water to its structure. Thus the
waterproof surface provides a barrier to water under all end-use conditions.
 CHAPTER 20 64

However in practice a waterproof fabric is generally required to allow no

penetration by water below a hydrostatic pressure of 100 cm (10 Kpa).
Waterproofing is achieved by coating the fabric with a solid polymer like
neoprene (synthetic rubber), polyvinyl chloride or polyurethane. Being non-
breathable, the waterproof fabrics are uncomfortable to wear because the
perspiration of the user is not permeated and dried due to nonporous nature
of the material. The coated materials are therefore mainly used for
commercial and industrial purposes.

20.3 CONDITRIONS FOR HIGH WATER-REPELLENCY FOR

FABRICS High levels of water-repellency on fabrics depend upon the
following factors.
1. Fineness of yarn and close packing of textile structure.
2. A thoroughly prepared fabric surface that is free from impurities like
size or surfactants that have rewetting properties. Removal of
impurities helps in bringing the repellent chemicals in close contact
with the fabric surface. Shearing and singeing of the fabrics also
serves the same purpose.
3. Uniform application of the repellent-finish to provide a low-energy
surface that has a lower critical surface tension than the surface
tension values of water (and other liquids against which the repellent
finish is required).
20.4 CHEMICAL NATURE OF WATER-REPELLENT FINISHES
The water-repellent chemicals for the textile materials, as developed over the
years, are of a very diverse nature. The more important of these are
mentioned below although only a few of these are used for the protein and
the synthetic fibres.
20.4.1 Metal salts like Aluminium Acetate (CH3COO)3 Al: This is one of
the earliest compound used to impart water-repellency to cotton canvas
fabrics. Its application consists in padding or treating the fabric with a
solution of 5-90Tw. aluminium acetate or formate, followed by drying.
During drying, the aluminium salt is converted into water-insoluble
aluminium oxide (Al2O3) to make the fabric water-repellent. The main
problem with the finish is its tendency to dust off the fabric and so this led to
 CHAPTER 20 65

an improved method of depositing another aluminium compound that is

usually called, a technically incorrect name, the aluminium soap.

20.4.2 Soap and Metal Salts: In this method water-repellency is achieved

by depositing, inside the fabric interstices, insoluble and hydrophobic
aluminium soaps that are produced by reacting soaps with soluble
aluminium salts. The double-decomposition reaction may be represented as
under:

3 C17H35COONa + (CH3COO)3 Al → (C17H35COO)3 Al + 3 CH3COONa

The treatment may be carried out in a jigger or a winch but use of a padder is
preferred because it is more productive. The well-prepared cotton fabric is
impregnated with 2-5% soap solution at 600C, dried, and then padded again
in 5-90 Tw aluminium acetate solution. The fabric is next rinsed to remove
sodium acetate formed during the reaction and then dried at a high
temperature for proper penetration of the metal soap (aluminium stearate)
into the fibres and the fabric interstices.

To simplify the two-stage procedure, the fabric may be padded, using a

sturdy padder, in a viscous solution of pre-prepared aluminium stearate
[(C17H35COO)3 Al] in the white oil. Alternatively, the fabric can be padded in
the molten aluminium soap. This method is generally confined to preparing
heavy waterproof canvas fabric required to cover equipment lying in the
open or for tents and awnings. Usually 0.5% of a copper salt, commonly
copper nepthenate is added for protection against microorganisms (rot
proofing). Sometimes mineral wax is also added to the stearate to make the
waterproofing still more effective.

20.4.3 Wax Applications: Different mineral and natural waxes have been
used for the water-repellent finishes but these are now being replaced with
the chemically more complicated and also the fibre-reactive compounds that
yield more lasting finish. The waxes commonly used are, a) mineral wax
(alkanes-melting point 52-560C), b) beeswax C15H31COOC30H61, (m. pt. 62-
650C) and c) Carnauba wax C25H51COOC30H61, (m. pt. 83-860C). The waxes
are applied by different methods as mentioned below.
 CHAPTER 20 66

i) Dissolving wax in an organic solvent and applying by a lick roller or

by spraying, followed by drying. The method is now ecologically
unacceptable.
ii) Rubbing fabric against wax bars followed by hot calendaring.
iii) Spraying molten wax with steam jets and drying on hot cylinders.
iv) Padding fabric in an aqueous wax emulsion, drying and then melting
the wax for its even redistribution.
20.4.4 Pyridinium-Based Quaternary Ammonium Hydrocarbons: These
are represented with the following structure.

- C l
+
5 H 5N C w h e r e n r a n g e s b e t w e e n
2 O n HC 2 n + 1 C H

It is considered that during heating, thermal decomposition of the pyridinium

salt takes place and the liberated chloralkyl ether reacts with the hydroxyl
group of cellulose as indicated below.

Heat → C5H5N + C17H35OCH2Cl + CellOH→ CellOCH2C17H35 + HCl

The most well known examples of this type of compounds are Velan PF
(ICI) and Zelan AP (du Pont) that are considered to be stearamidomethyl
pyridinium chlorides. The oily chains were supposed to form covalent bonds
with cellulose molecules but later studies showed that only a part of the
compound was covalently linked with cellulose. However it was enough to
impart fairly permanent water-repellency along with a soft handle to the
fabric. These compounds are applied with sodium acetate that converts the
strong mineral hydrochloric acid liberated during the reaction into the non-
damaging acetic acid and thus serves to protect the cotton fabric from the
possible hydrolytic damage.
The main problem with such water-repellents is liberation of pyridine, which
has an unpleasant odour and is also toxic, and so ecologically undesirable.
20.4.5 Organo-Metallic Complexes: These compounds contain chromium,
aluminium or copper atoms complexed with stearic or myristic acids and
impart semi-permanent water-repellency to both the natural and the synthetic
textiles. These are dissolved in isopropanol, and are applied by pad-dry-cure
 CHAPTER 20 67

method. The metal ions are supposed to form bonds with the fibres and the
hydrophobic fatty components are oriented towards the surface of the fabric.
The more effective copper-complex also imparts the anti-microbial property
but gives a green colour to the fabric. The colour restricts its use mainly to
tents, awnings, boat covers, surgical gowns etc. The chromium complex is
not much used on textiles and its main application is on leather and paper.
20.4.6 N-Methylol Derivatives: These self-cross linking or cyclic reactant
compounds like dimethyloldihydroxyethylene urea (DMDHEU) or
trimethylol melamine have been used on the cellulosic materials for
imparting crease-recovery property since long. By incorporating a
hydrophobic fatty chain in the molecules of the reactant C.R. agent, a
durable water-repellency is obtained along with the crease-recovery
property. Wax is often added to increase the effect.
O

Usually an add-on of 3-4% is needed to get effective results, which is

applied by padding, followed by drying and curing at 1500C for 1-2 minutes.
The finish however is not completely fast to dry-cleaning.

20.4.7 Silicone Finishes: Siloxanes are extensively used as softeners in the

textile industry and are known to be mildly water-repellent. On curing, the
dimethyl derivative, provides good hydrophobicity along with soft handle to
the fabric but its complete polymerisation requires a long time at elevated
temperatures (200-2500C). To lower the curing temperature, methylhydrogen
silicone is copolymerised with the dimethyl derivative and the resultant
product can be cured at 120-1500C for only a few minutes. The copolymer is
therefore commercially acceptable but the handle becomes slightly harsh.
The structural formulae of dimethyl and methyl hydrogen polysiloxanes and
their copolymer are shown below as (a), (b) and (c) respectively.
 CHAPTER 20 68

3
C 3 H C 3 CH H C 3 H C 3 H C 3 H

3 S H i - S OC i - O S iC 3 HH 3 C+ S i S iO - O C 3 HS i
3 C 3 H n C 3 HC H H H n
H

( a ) ( b )

3
C 3 H C 3 HC HC 3 H

3 S H i - S OC i - OS i - O S iC 3 H

3 C 3 H x H C Y CH 3 H
( c )

In addition to a balanced mixture of the two siloxanes, the water-repellent

formulation contains catalysts of zirconium, titanium or other compounds.
These are not catalysts in the sense as to enhance rate of polymerisation but
these tend to orientate or direct oxygen atoms in the silicones towards the
fibre surface for chemical bonding and the methyl groups away from the
surface for water-repellency. The optimum results are obtained by ‘ageing’
for 24 hours after curing when the crosslinking process is completed.

Polysiloxanes are soluble in many organic solvents like xylene and also the
more economical tetrachloroetylene, and so can be applied in the special
solvent-applicant machines with arrangement for recovery of the used
solvent. This method gives enhanced water-repellent effect than that
obtained with the aqueous emulsion process.

The durability of silicone finishes is fairly high to the normal laundering and
dry- cleaning but its quality deteriorates on repeated laundering because the
fibres swell on wetting and the hydrophobic surface-film develops cracks,
through which water can seep.

Polysiloxane finishes are popular because of ease in their application, a

relatively low add-on, soft handle, compatibility with other chemical
finishes, applicability to different textile materials and above all lower cost
as compared with the other permanent finishes. The silicones are often
 CHAPTER 20 69

replaced with the fluorochemicals, which though expensive, are more

acceptable on account of the combined water and oil-repellency properties.

20.4.8 Fluorochemical finishes: The fluorochemicals or fluorocarbons are

best known for their stain and oil-resistant characteristics but these also have
outstanding water-repellent properties. These extraordinary chemicals have
been successfully exploited for the combined effects of stain and water-
repellency.

The fluorochemicals are often mixed with the common water-repellent

hydrophobic compounds for a synergistic effect. The complex formulations
are marketed as aqueous emulsions for ease in their application by the
padding techniques. The chemical add-on is around 0.15-0.3% on the weight
of fabric. After impregnation, the fabric is dried at 110-1300C and then cured
at 160-1800C for 45-30 seconds.

20.5 WATERPROOF BREATHABLE FABRICS

As mentioned earlier in section 20.2, the waterproof fabrics completely
prevent penetration of liquid water whereas the water-repellent fabrics only
delay the penetration of water. However water repellent garments are more
comfortable to wear because these allow the perspiration of the wearer to
gradually permeate out giving a feeling of dryness to skin.
The breathable fabrics allow passive diffusion of water vapours but the
fabric can still prevent penetration of liquid water. These have been
developed on the consideration that diameter of the smallest raindrop is 100
µm and cannot pass through holes of about 10 µm while molecules of water
vapour having a diameter of 0.0004 µm can permeate.
Waterproof breathable fabrics may be divided into the following three types;
i) densely woven fabrics with maximum pore size of 10-4 µm.
ii) laminated membranes with maximum pore size of less than 0.001µm.
iii) coatings with maximum pore size of 3 − 0.1 µm.

20.5.1 Densely Woven Fabrics: The earliest fabrics of this type were
developed in 1940s for military purposes and were termed as “ventile
fabrics”. These are made from combed yarns spun from fine cottons that are
 CHAPTER 20 70

then plied to make yarn as smooth and regular as possible. The yarn is
converted into fabric with Oxford weave (plain weave with two threads
woven as one in the warp) to give the weft yarn minimum crimp and to
make fibres parallel to the fabric surface. On wetting, the fibres swell to the
maximum extent that results in decreasing the size of the pores in the fabric
from 10 µm to 3-4 µm across. With a fabric density of about 100/cm, these
ventile fabrics effectively resist penetration of water from the medium
intensity rain showers.
Microfilament yarns of polyester or polyamide with diameter of less than 10
µm are also used to make densely woven fabrics that are waterproof
breathable. To further improve their hydrophobicity, these may be treated
with silicone or fluorochemical finishes, but the treated fabric still remains
permeable to moisture vapour.

20.5.2 Laminated Membranes: Membranes for water repellent purposes

are manufactured as thin polymeric films of 10 µm thickness and are
laminated to the conventional textile fabric to provide a suitable barrier to
liquid water. Such microporous membranes may be made from a film of
polytetrafluoroethylene polymer that is claimed to have 1.4 billion holes per
square centimetre. These membranes are usually supported with a layer of
hydrophilic polyurethane or modified polyester film. The hydrophilic
membrane though non-porous absorbs water (perspiration) and acts as a
porous conduit for water vapours and also decreases effect of the oily
contaminations of the human body on the water repellent membrane.

20.5.3 Coatings: These are both microporous and hydrophilic types and may
be produced by wet coagulation, thermocoagulation or foam coating
methods. These coatings form a large number of interconnected channels
that allow the water vapours to permeate.

A special coating (Stomatex) has been introduced by Akzo Noble, which is a

closed foam insulating neoprene film incorporating a series of small convex
domes that are vented by small apertures at the dome apex. These apertures
open and close like plants (leaf stomata). This film works in conjunction
with a waterproof breathable membrane and thus provides a strong
breathable structure with a high comfort level.
 CHAPTER 20 71

20.6 Waterproofing: The waterproof fabrics are mainly used as covers for
military hardware and other commercial materials to protect these from rain
showers. The earlier methods of making textile fabrics impervious to water
were crude and consisted in application of natural vegetable products like
rubber latex exudations and linseed oil. By the beginning of the 19th century,
chemically modified materials were introduced and aluminium soaps either
alone or in admixture with wax and fat emulsions were extensively used. As
the latex emulsions did not give very satisfactory coatings, these were mixed
with mineral waxes and animal fats like stearin. In an alternative process that
is still popular, the latex solution is mixed with a vulcanizing agent, fillers
and accelerator to form an adhesive rubber film on the fabric. This technique
is used for backing of rugs and carpets and also on the canvas transmission
belts, hoses, gum boots etc. The heavy tarpaulins for the military hardware
used to be coated with a solution of tar, pitches and wax dissolved in naptha.
These were often mixed with lithopone (a mixture of zinc sulphide and
barium sulphate) and other pigments and the total add-on would be in the
range of 30 to 35%. These have now been replaced with the lighter-weight
and less messy products, as mentioned before.

20.7 FLAME-RETARDANT FINISHES

All textile fibres are destroyed by fire and produce heat and suffocating
fumes that cause injuries and death to the all forms of life- human, animal
and others. A great deal of work has therefore been done to learn about the
mode of destruction of fibres by fire and to devise methods to minimise the
damage to life and property originating from accidental fires. Methods used
for protection of flammable materials from fire dates back to about 400 B.C.
The earliest recorded attempts for prevention of fire to textiles were made in
1640 when clay and plaster of Paris were applied to canvas used in theatres.
To these formulations, alum and ammonium phosphate were added about a
100 years later. The first scientific investigation was perhaps carried out by
Gay Lussac in 1820 and he concluded that the most effective salts for
‘fireproofing’ were either those that covered the fibres with a glassy layer or
those which produced non-flammable vapours on heating. In the later case
the vapours extinguish the fire by excluding oxygen near the flame.
 CHAPTER 20 72

However these explanations for fireproofing do not explain all the

observations. The term ‘fireproofing’ tends to imply that the fireproofed
fabric when brought in contact with flame will behave like asbestos.
However main aim of ‘fireproofing’ is to suppress the tendency of the textile
materials to spread fire and not to protect it from the fire damage. Actually
such treatments tend to increase the rate of destruction of the fibres. The
more accepted term now for avoiding the fire hazards of textiles is flame-
retardancy.

A great deal of work has been done in recent years to understand the mode
of combustibility of different textile fibres and the factors responsible for
propagation of fire. Burning behaviour of the different textile fibres may be
summed up briefly as follows. The cellulosic fibres are charred and produce
heat and volatile products; the latter catch fire and further spread the fire.
The charred matter has the property of ‘afterglow’ (flameless or smouldering
combustion) that rekindles the fire after extinguishing it. The synthetic fibres
like polyester and nylon melt and catch fire producing a smoky flame.
However the fibres shrink away from the flame and the molten mass drips
down thus removing heat from the flame front and reduces chances of
propagation of fire. This is in contrast to burning of cotton as discussed
above. However the flaming-drippings can spread fires separately if these
fall on carpets, or other combustible materials. Besides these drips cause
severe burns to living beings that may come in contact with the melt-
drippings. In composite textiles like Polyester/cotton, a blend of
thermoplastic and non-thermoplastic materials, the former melt on ignition
but spreads flame on to the cotton component that propagates it by the so-
called scaffolding effect.

The protein fibres like wool and silk catch fire but do not propagate the
flame and are self-extinguishing when moved away from the flame. Fabrics
of protein fibres are therefore considered to be safer than those of other
fibres and are specifically recommended for children’s night-ware. The
inherent good flame-retardancy of wool is due to its high contents of
moisture (16%), nitrogen (15%) and sulphur (3-4%) and low content of
hydrogen (6-7%). Nevertheless wool materials are given the flame-retardant
 CHAPTER 20 73

treatments when used for the aeroplane seat covers to meet the stringent
safety requirements.

From the above it is clear that each group of chemically different fibres
require some specific flame-retardant finishes that are compatible with their
chemical natures. A brief review of the existing flame retardant treatments is
given below for different types of fibres.
20.7.1 Cellulosic Fibres: In principle any Lewis acid forming substance will
promote flame retardancy by inducing char formation and many common
acid salts have been used since long for this purpose. However the ideal salt
should not generate acid below 1500C i.e. during the usual drying and curing
stages. A large number of proprietary products, both organic and inorganic,
have been marketed that have varying degrees of durability. These include
boron, antimony and ammonium salts and organic compounds containing
phosphorous, nitrogen and bromine. The marketed formulations usually
contain both inorganic and organic compounds in different concentrations.
Some of the more common flame-retardants are briefly discussed below.

One of the earlier non-durable inorganic flame-retardant is a mixture of

borax (Na2B4O7) and boric acid (H3BO3) in a 7:3 ratio with add-ons of 10-
15% but this suffers from poor after-glow retardancy. Another common non-
durable finish is diammonium phosphate {(NH4)2HPO4)} but it has now been
almost completely replaced with a more durable ammonium polyphosphate
(APP) whose durability increases with increase in the molecular weight of
the polymer. The phosphorous in these two compounds reacts with cellulose
(phosphorylation) that improves durability of the finish but an add-on of 1.5-
4.5% phosphorous is required for adequate protection against spreading of
flame. Fire-retardancy of APP is further improved by addition of urea that
has a two-fold function. Firstly urea enables APP to be cured at a relatively
high temperature of 1500C and this increases degree of phosphorylation of
cellulose and consequently durability of the finish. Secondly urea, by virtue
of its swelling action on cellulose fibres, improves penetration of APP in the
fine structure of cellulose and provides more uniform and better effect. Some
organo-phosphorous compounds were also developed that would react with
cellulose at about 1500C to impart a wash-resistant flame-retardant finish.
Chemical structures of three phosphorous compounds are indicated below.
 CHAPTER 20 74

O
O H C CH 2
C H 2 O H
2
N P N
H O– –P O– H 2 C C H 2
H O2 HP +
CC 2 H O H C l
N
N 4H C H O H
H 2 C C H 2
2

Ammonium Polyphosphate Tris(1-aziridinyl) Phosphine Oxide Tetra kis hydroxymethyl

Phosphoniumchloride
APP A.P.O (T.H.P.C.)

A large number of proprietary products, both organic and inorganic as well

as their mixtures of varying durability, are available in market and most of
these formulations contain nitrogen, phosphorous and halogens (mainly
bromine) in different proportions. An interesting development is the use of
crosslinking silicone combined with compounds containing nitrogen and
phosphorous. This finish is fairly durable and is popular for back-coating
outdoor fabrics like tents and curtains in theatre and cinema houses. The two
most popular products that are durable for at least 50 launderings are
marketed under the names of Pyrovatex CP (Ciba), Pekoflam DPM
(Clariant) or Amgard TFR 1 (Rhodia) and Proban CC (Rhodia, formerly
Albright and Wilson).

Pyrovatex CP is a cellulose reactive methylolated phosphonamide of the

following chemical structure.

The fire retardant Pyrovatex CP is bound with cellulose molecules via

reactive resins like methylolated melamine or dihydroxydimethlolethylene
(DHDMEU) in the presence of an acidic catalyst. A typical recipe consists
of 280 g/I Pyrovatex CP, 35g/I methylolated melamine, 25g/I
Orthophosphoric acid (catalyst) with a softener and a wetting agent. The
chemistry of reaction may be represented as under.
 CHAPTER 20 75

The fabric is carefully padded or foam-applied with the liquor, dried at

1300C and cured at 1500C for 4-5 minutes or at 1700C for 1 minute.
Generation of formaldehyde and other volatile compounds during the
reaction is a serious drawback but is contained by scrubbing the volatile
products with water. To neutralise any acid, the fabric is treated with an
alkaline solution at 500C and then washed and dried. The treated fabric binds
1.5-2% phosphorous to get a fairly permanent flame retardancy and also
acquires some crease recovery property with only about 20-25% loss in
tensile strength. The fabric remains compatible with dyes and is superior to
Proban CC in this respect.

Proban CC is a THP salt-urea complex {(CH2OH)3P+(Cl-)CH2NHCONH2}

that requires an ammonia cure and a final oxidative treatment with hydrogen
peroxide. The complex is applied along with wetting and softening agents by
a pad or foam application method, dried with a moisture content of 8-10%
and then exposed to ammonia vapours to create crosslinks between THPC-
urea complex chains. The reaction yields an insoluble polymeric phosphine
having a molar P:N ratio of 1:2. The resulting phosphine polymer has a
highly reducing nature and is oxidised with dilute hydrogen peroxide to
stabilise it as an oxide. The treated fabric acquires some stiffness but
becomes softer after laundering that removes the surface polymer. The
chemistry of the possible reaction is given below.
 CHAPTER 20 76

The above two proprietary products are fairly permanent and are so far
known to have no toxic effects but are expensive. The high cost of these
products has given rise to use of relatively less durable but inexpesive
expensive halogenated hydrocarbons especially for the back-coated outdoor
fabrics like tents and tarpaulins. A common and economical product is
chlorinated paraffin waxes {CnH(2n-m+2)Clm}. More recently back-coating
formulations comprising antimony-bromine compounds present in acrylic
resins have become popular. A typical recipe consists of 3%
decabromodiphenyl oxide (DBPO), 17% antimony oxide (Sb2O3) and 50%
acrylic binding resin to get a mole ratio for Sb:Br of 1:3. The commercial
product may also contain antifoaming agent, viscosity modifiers etc. The
fabric is back-coated with the mix and dried. An add-on of 20-30% is
maintained in the finished product to get the optimum result.
 CHAPTER 20 77

20.8 ENVIRONMENTAL IMPACT OF FLAME-RETARDANT

FINISHES: The above mentioned flame-retardant chemicals are not
environment and friendly especially antimony, halogen and even
phosphorous compounds. A great amount of work is going on to reduce the
impact of these compounds on the environment and more efficient methods
have been developed to minimise waste and also to recycle the by-products.
Improvements have also been made in the scrubbing systems for containing
formaldehyde and other toxic vapours and to eliminate their escape to the
atmosphere. Special efforts are being made to reduce antimony and bromine
(Sb-Br) concentrations in the back-coatings or to entirely replace these with
ammonium polyphosphate formulations. Another interesting development is
the introduction of intumescent products that is briefly discussed below
because much information of the chemicals is not available as yet.

20.9 INTUMESCENT APPLICATIONS

Intumescence is a phenomenon where heat or some other agent promotes
formation of an expanded or a swollen condition; in case of the flame-
retardant this is an expanded char. Intumescent coatings applied to the textile
fabrics are activated with heat and generate a flame-resistant foamed layer
on the fabric surface that stops or retards propagation of flame.

Intumescent coatings contain four major components-a char former

(carbonific), a catalyst, a ‘spumific’ or gas former and a binder. On heating,
the binder melts and spreads to form a skin over the fabric surface and thus
protects the inner layers from oxygen in atmosphere and so combustion is
avoided. The heat then activates the catalyst, which decomposes to yield an
inorganic acid and chars the carbonific compound by a dehydration
mechanism. At the same time heat makes the intumescent compound
generate non-flammable gases, which are trapped within the viscous
carbonaceous char, blowing up the layer to form a thick thermally-insulating
foam. This foam acts as a char-barrier and mechanically resists spread of
flame and also reduces emission of smoke and other toxic emissions.

In a more recent work, a mixture of ammonium and melamine phosphates

and intumescents applied in a resin binder to cellulosic fibres imparts such a
high flame-retardancy that is comparable with the performance of aramid
 CHAPTER 20 78

fibres. These finishes are equally effective on wool and polyamide fibres.
Presently a lot of research and development work is going on intumescent
flame-retardant-complex finishes as substitutes to ecologically unacceptable
formulations like Sb-Br compounds. It is expected that in the next few years
there will be increased use of the intumescent-based compounds.

20.10 PROTECTION AGAINST MICROBIOLOGICAL DEGREDATION

Spores of fungi and bacteria exist everywhere and under hot and humid
conditions these rapidly multiply feeding on their hosts. In case of textiles,
these microorganisms attack the natural fibres as well as the finishes applied
to these and cause mildew and rotting damages. The enzymes that degrade
cotton are cellulase and cellobiase and these reduce strength, produce
coloured and foul smelling spots and even holes on the exposed fabrics. It
appears that accessibility of the hydroxyl groups of cellulose to the
microorganism has something to do with the damage because the viscose
rayon with greater amorphous content than cotton is more susceptible to
damage while the acetate is immune to their attack.

Among all textiles, cotton goods are most exposed to the mildew damage
because these being less expensive and more durable, are extensively used
for the outdoor requirements like covers, tents, awnings, screens, sail cloth
etc. Even otherwise, these are liable to damage during storage and
transportation over high seas especially when starch is present in their
finishes. A lot of work has, therefore, been done to develop effective yet
economical antiseptics for cotton and now a variety of inorganic, organic
and organo-metallic compounds are available for this purpose. Ideally an
antiseptic should be colourless, odourless, nonvolatile, non-toxic to human
beings, efficient in low concentrations and above all have a low cost. It is
understandable that such a perfect product has not become available as yet
but a few of the important antiseptics are discussed below in a more or less
chronological order of their development.

20.10.1 Inorganic Compounds: It is well known that certain metal cations

like copper, zinc and cadmium are toxic to microorganisms and fabrics are
protected by a simple treatment of padding in solutions of salts of these
metals followed by drying at a low temperature. However these salts are not
 CHAPTER 20 79

wash-resistant and also reduce strength of the material during drying. The
most successful compound in this category is cuprammonium hydroxide that
is prepared by dissolving cupric hydroxide in concentrated ammonia liquor.
The solution applied by the padding method dissolves the surface layers of
cellulose fabric and the copper compound is deposited there. The material
acquires a greenish colour but otherwise has a very good antimildew
property. On squeezing the softened fabric between rollers, the fabric-
interstices are closed forming a water-resistant film and so a combined water
and mildew-proof finish is obtained. This treatment, known as the Willesden
finish, had been extensively applied to heavy canvas fabrics meant as covers
for military hardware but has now been replaced with other chemicals.
20.10.2 Organic Compounds: Simple organic compounds like phenol,
formaldehyde and salicylic acid were known to have antiseptic properties
since long and initial trials were made with these for the light-weight fabrics.
However these are deficient in one respect or the other. Formaldehyde has
an unacceptable pungent odour besides being toxic in high concentrations.
Phenol is coloured and salicylic acid becomes ineffective on coming in
contact with alkalis. However more complex derivatives of these compounds
have been found effective even in low concentrations (0.02 to 0.05%) and
have comparatively better wash resistance. More common among these are
salicylanilide (Shirlan), pentachlorophenol and paranitrophenol, 2,2'-
dihydroxy 5,5' dichlorodip-henylmethane (G4).
O H O H O H H O H
O HH C l C l C
C N H
C l C l
O C l
N 2 O C l C l
S h i r l a n P e n t a c h l o Pr o a p r ah ne ni t o r lo p h Ge n 4o l

Quaternary ammonium compounds having halogen or sulphur atoms in their

molecules posses good antiseptic properties and are popular for sanitization
of diapers to prevent baby rash. In a process similar to acetylation of surface
layers of fabrics, protection from mildew can also be obtained by
cyanoethylation reaction that unlike acetylation is uniform and does not
 CHAPTER 20 80

lower strength of the material. The reaction is carried out on cotton fabric
treated with caustic soda solution of mercerizing strength as shown below.

C6H9O4OHa + CH2=CHCN → C6H9O4OCH2CH2CN

It was learnt that a fixation of at least 3.5% of nitrogen gives the required
resistance to the microbiological attack. Understanding the role of nitrogen
led to use of simpler and consequently cheaper reagents like trimethylol
melamine by the pad-cure method.

20.10.3 Organometallic compounds: A large number of organometallic

compounds are mentioned in literature but perhaps the more successful ones
are copper nepthenate, copper soaps (copper oleate and stearate), cadmium
soaps, copper 8-quinolinolate (copper ions chelated with 2 molecules of
hydroxyquinoline) and mercury salicylate. A two-bath process using 1%
soap solution and copper or cadmium salt solution produces the metal soaps.
Copper napthenate is extensively used for heavy canvas fabrics along with
wax for a combined water and mildew proofing. Reacting copper salts with
napthenic acid, a cycloparaffin derivative obtained from petroleum, produces
copper napthenate. Use of tributyl tin, another organometallic compound to
be used in concentration of about 0.02%, is also mentioned in literature as a
bactericidal for the baby diapers.

20.11 FRESHNESS TREATMENTS

M/s Huntsman have introduced a new and interesting concept in textile
finishing in which they claim to covalently link ‘open’ micro-capsules to the
textile fibres. These capsules, termed as ‘empty pockets’ by the
manufacturers, can be filled with various freshening products like
deodorants, perfumes, antimicrobial chemicals etc that may withstand a
number of launderings. Chemically the open-capsules are prepared from a
cyclo-dextrin that is biodegradable and so is eco-friendly. These can be
attached to fabrics both by a batch or a continuous process. The product is of
considerable interest and may find application in certain fashion garment
trades.
 CHAPTER 20 81

ADDITIONAL READING MATERIAL

1. Textile Finishing, Ed. Heywood, D, Society of Dyers and Colourists, Bradford, 2003.
2. Marsh, J.T., Introduction to Textile Finishing. 1966, Chapman and Hall, London.
3. Whewell, C.S., The Finishing of Textile Fabrics, Textile Progress, 2, No.3. !971-72.
4. Idem., Advances in the Finishing of Textiles, Review of Tex. Progress, 14, 1984.
5. Colorants and Auxiliaries, Volume 2, Ed., Shore, J., Society of Dyers and Colourists,
Bradford, 2002.
6. BASF, Textile Finishing Manual. 1973.
7. Smith, The Chemical Finishing of Textiles, Rev. Prog. Coloration, 6, 1975.
8. Shenai, V.A. and Saraf, N.M., Technology of Finishing, 1987. Sevak Publications,
Bombay, (India).
9. Harrison (Ed.), Textile Finishing, 1978. The Textile Institute, Manchester.
10. Hall, A.J., Textile Finishing, 1966. Tingling & Co, London.
11. Textile Series Reports. U.S. Quarter Master Corps.
12. Technical Literature of Textile Auxiliaries Manufacturers.
13. Little, R. W., (Ed.) Flame Proofing Textile Fabrics. Reinhold, New York, 1947.