39

Water Resistant-Breathable
Hydrophilic
Polyurethane Coatings
V. M. DESAI AND V. D. ATHAWALE*
Department of Chemistry
University of Bombay
Vidyanagari, Bombay
400 098
India
ABSTRACT:
Polyurethane (PU) coatings
on
nylon
fabric that have
high
moisture
permeability
and water
repellency properties
have been
developed.
These PU
coatings
are
prepared by reacting ∈-caprolactam-4,4-diphenyl
methane
diisocyanate
(MDI)
adduct with
hydrophobic polyols; subsequently deblocking
of
∈-caprolactam
was carried out
using polyethylene glycol (PEG)
of different molec-
ular
weights
at ambient
temperature.
The
hydrophobic
and
hydrophilic segment
bal-
ance was
adjusted by changing
the molecular
weight
of PEG to
impart optimum
moisture
permeability properties.
KEY WORDS:
∈-caprolactam, deblocking, polyurethane,
moisture
permeability
and water
repellency.
INTRODUCTION
HE
POLYURETHANE
(PU)
coatings
are now
successfully
used in a wide
variety
of
applications [1]. Polyurethane
textile
coatings,
however,
are
becoming increasingly important
because of the
unique
effects that
they
make
possible [2].
In the last few
years, major
inventions and
improvements
have been made in
waterproof
breathable fabrics
[2-4].
There are several
methods
by
which
breathable-waterproof
fabric can be
prepared,
such as
*Author to whom
correspondence
should be addressed.
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1995
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40
microporous, hydrophilic,
and the fabric based on microfilaments
[5].
The
advantage
of
hydrophilic polyurethane coatings
over laminated and micro-
porous polyurethane
film is that the former has
good
adhesion on textile
substrate,
high gloss,
water and solvent
resistance,
high
moisture
permeable
properties
and it is less
expensive.
A tremendous
growth
in the
synthesis
and
application
of
hydrophilic polyurethane coatings
in various
disciplines
was
recently patented [6-9].
The
hydrophilic
PUs are manufactured
by
the com-
bination
of hydrophobic
and
hydrophilic polyols
with
diisocyanate compo-
nents to
produce optimum
moisture
vapour
transmission
properties
without
loss of other
physical properties. E-Caprolactam
blocked urethanes have
been studied
extensively
for
coating applications by
several authors
[10-12].
Generally,
in
one-pack coating system,
blocked
polyisocyanates
are used
due to some technical and economical reasons. The traditional
way
of react-
ing
a blocked
isocyanate system
is that the
deblocking
of the
caprolactam
occurs in the first
step
to form
isocyanate,
followed
by
reaction with
polyols
to form
polyurethane.
It has been
reported
in the literature that
polyethylene
glycol
can be utilized as a
deblocking
aid with
e-caprolactam [13]. Using
this
approach,
in the
present study,
various
polyethylene glycols
of molecular
weight
400, 1000,
3000 and 6000 were used to
prepare hydrophilic
polyurethane coatings.
These
polyurethanes
were
prepared by
the reaction
of
polyester polyol
based on castor oil and
E-caprolactam-4,4-diphenyl
methane
diisocyanate (MDI)
block
prepolymer.
The
deblocking
of
e-cap-
rolactam was carried out
by polyethylene glycols
at ambient
temperature.
The resultant
hydrophilic polyurethane
was coated on
nylon
fabric to
get
water-repellant
moisture
permeable properties.
MATERIALS AND METHODS
All the raw materials used in this
study
are listed in Table 1. The
polyols
and
polyethylene glycols
were dried and
degassed
in vacuum at 100C
prior
to use.
Castor oil based
polyester polyol
was
prepared by reacting
castor
oil,
adi-
pic
acid and
trimethylol propane by
condensation
polymerization technique
under
nitrogen atmosphere
at 180-220C. The reaction was monitored
by
the
change
in acid value with time.
e-Caprolactam
was reacted with
4,4-
diphenyl
methane
diisocyanate
at 30C under
nitrogen atmosphere.
The
reaction was carried out in
xylene
solvent for 3-4 hours until constant %
NCO was obtained.
Finally, E-caprolactam-MDI prepolymer
was
stoichiometrically
reacted with
polyester polyol
to
produce e-caprolactam
block
polyurethane.
The
completion
of the reaction was confirmed
by
the
absence of NCO band at 2270 cm- in the infrared
(IR) spectrum.
41
Table 1. Raw materials.
Preparation
of
Hydrophilic Polyurethane
The
e-caprolactam
blocked
polyurethane
was mixed with
polyethylene
glycol, xylene
and
dibutyltin
dilurate as
catalyst
for
deblocking
reaction.
The
deblocking of E-caprolactam
was carried out at 130C under
nitrogen
atmosphere
to
get hydrophilic
PU. The
completion
of reaction was con-
firmed
by
IR
spectroscopy.
Application
of
Polyurethane Coating
A
processing
solution of solid content 80% was
prepared by dissolving
e-caprolactam
block
polyurethane
in
xylene-MEK (50% v/v)
and
mixing
with stoichiometric
quantity
of
polyethylene glycol
400. The solution was
applied
to scoured
nylon
fabric
(30
X 30
cm)
on one side
using laboratory
coating
table ERNST BENZ A. G. Model 350 KSV/MT-D
by
knife
coating
technique
to
get polyurethane
coated fabric
(PU1). Similarly
PU2, PU3,
PU4,
Polyurethane
coated fabrics were
prepared by using polyethylene gly-
col
1000,
3000 and 6000
respectively.
The
specification
of uncoated
nylon
fabric is
given
in Table 2.
- ,
Table 2.
Analysis
of
nylon
fabric.
42
The PU coated fabric was cured at 140C for 2 minutes in an oven
(model
ERNST BENZ
A.G.).
The fabric was further treated with water
repellent
fluorocarbon
(Scotchguard)
and cured at 120C for 1 minute.
Measurement of
Physical Properties
of Coated Fabric
(1)
Moisture
permeability:
The moisture
permeability
of coated fabric was
measured
by using
American
Society
of
Testing
Materials
(A.S.T.M.)
E 96 63-T
evaporation
method at 37C.
(2)
Water
repellency:
The water
repellency
was measured
by using
standard
rating
test recommended
by
American Association of Textile Chemists
and Colorists
(A.ATC.C.)
test
22-1977,
(1979).
(3) Water proofing property:
The water resistance
hydrostatic pressure
head test
was carried out
according
to A.A.T.C.C. test
127-1977,
(1979).
(4) Washing fastness:
The
washing
fastness of the coated fabric was carried
out
using
A.S.T.M. D-2724 standard method.
(5)
Tensile
strength
and
elongation:
The tensile
strength
and %
elongation
of
coated
nylon
fabrics were measured
by using
tensile
testing
machine
(Master
control R&D
electronics,
India) according
to A.STM. D-1775.
(6)
The cross sectional view
of hydrophilic polyurethane
material coated on
nylon
fabric was
photographed
on
photomicroscope, (Carl
Zeiss
Model,
West
Germany)
at
magnification
126
(Figure 1).
FIGURE 1. Cross-sectional view of
polyurethane
coated
nylon
fabric at
magnification
126.
43
Table 3.
Physical properties
of
polyurethane
coated
nylon
fabric.
RESULTS AND DISCUSSION
The
physical properties
of
polyurethane
coated
nylon
fabric are collec-
tively presented
in Table 3.
Permeability Properties
The moisture
permeability
of
hydrophilic polyurethane
is a function of
the
ethylene
oxide units
present
in the
system.
The
ethylene
oxide concen-
tration of the
system
is
proportional
to the PEG soft
segments [5].
The
moisture
permeability
of the coated fabric is
graphically represented
in
Figure
2 which shows increase in moisture
permeability
with the increase in
molecular
weight
of
polyethylene glycol.
The
dependence
of moisture
permeability
on molecular
weight
of
polyethylene glycol segment
indicates
that
hydrophilicity
of
polyurethane
can be varied either
by increasing
the
overall content
of hydrophilic component
or
by altering
the chain
lengths
of
the
hydrophilic segments.
The
rapid
diffusion of water
vapour
is facilitated
by
the low
binding energy
of
polyethylene glycol
chain
segments
for water
molecules
[4].
In the
present system
on one hand the
swelling
of the
44
urethane membrane
by
water
vapour
is
encouraged by hydrophilic
soft
seg-
ments
present
in
polyethylene glycol
and on the other hand
swelling
is re-
stricted
by hydrophobic
chain
segments present
in the castor oil based
polyol
to
prevent complete
dissolution of urethane
polymer
in water.
Water
Repellency
Wetting
of the fabric is a mechanism which
depends
to a
large
extent on
the difference between the adhesive forces between water and the surface in
contact and the cohesive force between the molecules of the water. The
water
repellency
of coated
nylon
fabric
gives
50%
rating (spray test)
due to
wetting
of surface in contact with the
water,
because the
present
polyurethane coating
contains both
hydrophobic
and
hydrophilic
chain
seg-
ments in
polymer
backbone. The castor oil based
polyester polyol
has
hydrophobic
chain which
imparts
water
repellency,
whereas the soft
seg-
ments of
polyethylene glycol having
water
absorption tendency
results in
50%
rating.
Therefore,
coated fabric treated with flurocarbon emulsion im-
proves
the
repellency up
to 90%
rating (spray test).
FIGURE 2. Relation between molecular
weight
of
polyethylene glycol
and moisture
permeability.
45
Washing
Fastness
The
washing
fastness of
polyurethane
coated
nylon
fabric was determined
by using
launderometer,
in
soap-soda
solution
(1:1)
for 30 minute at
60 t 1 C. The
washing
fastness was determined as % loss in
weight
of
polymer.
The
graphical representation
shows that
(Figure 3)
the
weight
loss
of
polymer
increases with increase in molecular
weight
of
polyethylene gly-
col. It indicates that the
hydrophilic polyurethane
looses its mechanical
property,
i.e.,
adhesive
strength
with increase in the
hydrophilic segments.
Tensile
Properties
The tensile
strength
of
hydrophilic
PU coated
nylon
fabric was found to
be on the
higher
side than uncoated
nylon
fabrics in both
warp
and weft
direction. The tensile
strength
is
dependent
on the thread
crimp
of
fabric,
denier,
coating quality,
location of the
coating
into the
interstices,
and hard
and soft
segments present
in the
polyurethane coating.
The %
elongation
of
FIGURE 3. Relation between molecular
weight
of
hydrophilic segments
and % loss of
polyurethane.
46
the PU coated
nylon
fabrics are found to increase in
warp
and weft direction
of fabric with increase in soft
segments
of
polyethylene glycol.
It is
logically
observed that %
elongation
of
coating
is
dependent
on hardness and
stiffness. As stiffness is increased the
elasticity
of
coating
must lead to
reduced
mobility
of the
composite
coated structure
causing
reduction in %
elongation
of PU coated
nylon
fabric.
CONCLUSION

One
pack e-caprolactam
block
polyurethane
has been
developed, by
the
optimization
of balance between the
hydrophobic
and
hydrophilic
chain
segments
in
polymeric
backbone. This method has been found to be most
convenient to achieve the modified
hydrophilic polyurethane coatings.
These
polyurethane coatings
can be utilized for
nylon
fabric to
impart
mois-
ture
permeability
and water
repellency properties.
These fabrics could be the
best substitute for
synthetic
leather cloths used in foul weather
garments
for
civilian and
military
sectors.
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