Progr Colloid Polym Sci (2005) 130: 114

DOI 10.1007/b107336
Published online: 3 June 2005

Springer-Verlag 2005

Ulrich Siemann

U. Siemann
LOFO High Tech Film GmbH,
Weidstr. 2, 79576 Weil am Rhein,
Germany
e-mail: dr.u.Siemann@lofo.com
Tel.: +49-7621-703-114
Fax: +49-7621-703-313

Solvent cast technology a versatile tool

for thin film production

Abstract The oldest technology in

plastic lms manufacturing, the
continuous solvent cast process, was
developed more than hundred years
ago driven by the needs of the
emerging photographic industry. In
the years after 1950, new lm extrusion techniques of thermoplastic
polymers became the dominant
production method for plastic lms
and the importance of solvent cast
technology has declined. Nowadays,
the solvent cast technology is
becoming increasingly attractive for
the production of lms with extremely high quality requirements. The
advantages of this technology include uniform thickness distribution,
maximum optical purity and extremely low haze. The optical orienta-

Introduction
From the end of the 19th century, the development of a
process for manufacturing thin plastic lms was tightly
linked to the emerging industry for movies and photographic lms. 5 mil (125 micron) lm was produced using
a discontinuous device with a caster moving over 200 feet
long glass plates at Eastman KODAK [1]. Soon, rst
patents were issued to cast celluloid lms on a moving
surface by the Celluloid Company in the United States
and patented in 1896 [2]. For economic reasons, Eastman
KODAK developed a continuous casting process
parallel to the Celluloid Company, resulting in a patent
infringement. KODAK switched over from the discontinuous to the continuous casting process about 5 years
later. At that time, photographic lm base was produced
from cellulose nitrate and campher as a plasticizer from

tion is virtually isotropic and the

lms have excellent atness and
dimensional stability. The cast lm
can be processed in-line with an
optical coating design. The tremendous growth of new liquid crystal
display applications has incited the
development of new materials and
improved processes for solvent casting and coating techniques. The key
elements of cast lm manufacturing
are explained, and technological details are discussed for dope preparation, die design, casting support,
lm drying and solvent recovery.
Main applications of lms made by
dierent polymer/solvent combinations are described.

solutions in solvents such as acetone, ether and alcohol

on wheels with diameters of 9 feet (2 meters) at a
maximum speed of approx. 150 feet/h (50 m/h). That
translates into about 50 square meters / hour. The knowhow required to manufacture highly stable huge steel
wheels with perfectly polished surfaces was perfected by
the Eastman KODAK Company over the next 100 years.
It was an interesting switch in industrial history, that
the competing European lm companies started some
years later with belt casting technology and even now
both manufacturing processes still run parallel in the US
and elsewhere. The use of an endless exible belt seemed
to oer certain advantages in terms of process speed. On
the other hand, the technology needed to produce belts
with a uniform thickness, invisible joints and polished
surface was not very far developed in the early 20th
century.

From 1907 onwards, the rst belt machines with

copper belts of 1 m width and 35 to 50 feet (12... 14 m)
length were installed by AGFA in Berlin [3]. The
development of this type of technology was triggered
by the diculty of drying the lm fast enough on a
wheel whose circumference was at that time restricted
to about 9 m. But casting speed is not necessarily a
direct function only of drying length at the casting
support. Initially, the belt machines did not run faster
than the wheel machines, because of Eastman
KODAKs more advanced technology. It should be
mentioned that back then, the cast lm production
process did not include solvent recovery! Because of the
highly ammable nature of nitrocellulose lms, other
materials were screened for photographical use. In the
early 20th century, cellulose triacetate in combination
with the plasticizer triphenylphosphate was identied
by Eastman as safety lm, but it took many years to
achieve a mass production because methylene chloride
as the most suitable solvent was not available at low
cost at that time. Since the mid 20th century, cellulose
triacetate turned out to be the most important material
to produce photographical lms and movies [4]. It has
taken many years for the solvent casting manufacturing
process to develop into a high precision technique [5].
Today, it is used for the production of engineering
plastics, optical lms, medical lms and sheet forming
for electronic applications. A sketch of the entire
solvent cast process on a belt line is shown in Figure 1.

Fig. 1 Production of solvent cast

lms

Key elements of solvent cast technology

Raw materials
For the raw materials of the dope making process there
are some obvious prerequisites.




The polymer must be soluble in a volatile solvent or

water
A stable solution with a reasonable minimum solid
content and viscosity should be formed
Formation of a homogeneous lm and release from
the casting support must be possible.

To provide these properties many process tricks are used

such as co-solvent systems, dissolution at overpressure,
use of special molecular weight distributions of polymers
or co-polymers, additives such as plasticizers, release
agents etc. Examples of dope composition for cast lm
products are shown in Table 1. Starting with the cellulose
derivatives used from the historical beginning of this
technique, processes for other high performance materials have been developed over the last 40 years. Water is
still a common solvent for food-grade lms made of
biopolymers or polyvinylalcohol. Typical additives used
to provide specic lm properties are antiblocking and
antistatic compounds, chelating agents, colours, electrical conductive substances, pigments etc. When adding
solid substances that can be processed as highly loaded

Table 1 Polymers and Typical Solvents for Casting Processes

Cellulose Nitrate
Cellulose Diacetate
Cellulose Triacetate (TAC)

Ether, Esters
Acetone, Methanol
Methylene Chloride, Alcohols

Polycarbonates
Polyethersulfon
Polyetherimide
Polyvinylidene uoride
PVC (Polyvinyl chloride)

Methylene Chloride
Methylene Chloride
Methylene Chloride
Acetone
Tetrahydrofuran
Methyl-ethylketon

dispersions, the rheological implications have to be

carefully monitored. Particle size distribution and lter
mesh size should be adjusted during handling. When
adding soluble solid or liquid compounds such as
plasticizers, the assumptions are the same as for bulk
polymers: solubility and stability in solution and in lm
formation process. It should be noted here that cast lms
can in most cases be re-dissolved and reused as raw
material. The solution or polymer lm is exposed to
relatively low thermal or mechanical stress throughout
the entire production process. As a result, degradation or
adverse side reactions are insignicant.
Dope preparation
During this step, the solid polymer in various geometrical
shapes such as akes, granules chips or powder is
dissolved in pure solvents or mixtures. In principle,
standard types of chemical process mixers can be used.
Due to the large dierence in viscosity from pure
solvents to highly viscous solutions the geometry of the
stirrer or paddle elements has to be carefully selected.
Horizontal and vertical mixing vessels can be used, and
the mixer elements may typically take the form of blades,
anchors, spirals etc. Heating and cooling management by
thermal jackets is generally required. Mechanical shear
rate and dope temperature has to be carefully controlled.
It inuences the quality of the dissolution process, the
formation of gel particles, solvent evaporation, skin
formation and the degradation of polymer chains. The
addition of plasticizer, additives, co-solvents, non solvents, pigments and similar substances should be considered, as should the subsequent dispersion or
dissolution step. Typically, viscosities change from
1500 mPas to 80.000 mPas during the dissolution process, solids concentration ranges between 5% and 40%
and temperatures can vary between room temperature
and the boiling point of the solvents. A dissolution
process at some bar overpressure and elevated temperature can be used for polymers with dicult dissolution
properties, e.g. PVC in THF. Dissolution time is

Polyimides

Dimethylformamide

Polyvinylalcohol
Methyl Cellulose
Starch derivatives
Gelatine

Water, Methanol
Water
Water
Water, Methanol

normally several hours. Depending on the specic

process, the de-aeration step can be done batch wise by
boiling in the mixing vessel or holding tank, by degassing
continuously in heat exchangers or by vacuum equipment. Dope degassing is required in many cases to
prevent air bubbles during the lm forming process. The
next step after dope preparation is solution clarication.
Depending on the handling system, a 2 or 3 step ltration
process and solution ripening in holding tanks are used.
Several processes run at slight over-pressure in the vessels
to avoid skin formation and loss of solvents, others at
slight under-pressure and with an exhaust system to
avoid solvent emissions during the heating and cooling
steps. The entire dope line, including tanks, pipes, lters
etc., needs precision temperature control. In specic dope
making processes, further additives such as colour
master-batches can be injected just before the casting
step to prevent the colour contaminating the dope line.
Special attention should be given to the ltration
processes. Frame and plate, candle type and back-ash
type lters are used. One of the big advantages of the
solvent cast technology is that ne ltration processes
with very small mesh sizes, e.g. metal screens, can be used
when lms without particle type defects are required.
Usually several ltration steps are subsequently used,
ranging from coarse to ne ltration. Pressure dierence
during the build-up of residues on the lter pads, which
are usually made of textiles, fabrics etc., has to be
checked. Dope clarity can be checked with in-line
instruments employing light diraction principles. Some
producers use lter aids to improve gel particle separation. The advantage of the plate and frame lters is that
they oer large surface areas, the disadvantage is
handling during make-up, cleaning and the removal of
waste from the contaminated lter pads. For safety and
environmental reasons, in line lter washing and backash cleaning operations have been introduced over
recent years. The dope pumps also need special care.
Aggressive solvents or compounds at an elevated temperature and pressure, abrasion by particles, pulse-free
feeding of dope even at elevated pressures are key factors
in selecting suitable pump types.

Fig. 2 Cross-section of a Belt

Machine

c1

c2

e
a = caster, die, hopper
b = steel belt
c1 = support drum (driven)
c2 = rear support drum (steered)
d = belt channel
e = drying air
f = film take-off

Casting process casting support

A cross-section of a belt machine is shown in Figure 2.
Typically, supporting belts are 1.0 to 2.0 m wide and 10
to 100 m long. Stainless steel belts are between 1.0 and
2.0 mm thick. The belt channel allows a stream of air to
ow in machine direction or counter direction. One of
the two pulleys or drums is connected to a drive that
requires extremely accurate speed control to avoid even
slight speed variations. One drum is connected to a servo
system that adjusts belt tension in order to ensure
constant atness and absence of belt movements
(vibrations) in the critical area just behind the caster.
Another important reason for tension control is the
expansion and dilatation of the belt length caused by
temperature changes. Belt machines need a guide system
because the belt tends to shift during operation. The belt
is guided by horizontal movements of the support drums.
Optical or inductive sensors provide signals proportional
to the belt edge oset. The signals are fed into the
tension/guide control system. The two bearings of the
2nd support drum are moved equal distances in opposite
directions to simulate centre pivoting. Many dierent
support materials have been used for belts: Copper,
silver-plated copper, chromium-plated steel, stainless
steel, metal coated with polyvinylalcohol or gelatin,
polyester lm, PTFE lm and other polymer lms. At
present the commonest support materials are stainless
steel and chromium-plated surfaces. Important items for
belt and drum machines are the materials heat
conductivity, the technical processes used to create the
required surface nish and the options for repairing
small surface defects. The release behaviour of the seminished cast lm from the support is pivotal to the
process. Moreover, the supporting belts and their
welded joints must be exible enough to ensure long-

term operation. Manufacturing a highly glossy belt

surface is a tedious process lasting several weeks. There
are not many suppliers of belts in the world. Typical
geometrical specications for the surfaces of stainless
steel bands are: stainless steel NC 22V, thickness
1.4 mm, thickness tolerance 20 microns, surface nish
Ra = 0.02 microns, Rt = 0,1 micron. Further, the
specication of the thickness variation of the welding
seam is very important and usually customer-specic.
The cast technique permits simple production of lms
with structured surfaces. The belt surface is clearly and
accurately replicated on one surface of the lm. The
techniques used to adapt the surface of the drums or
belts to highly glossy, structured or matt lm nishes are
proprietary methods that have been developed over
many years.
A cross-section of a drum casting line is shown in
Figure 3. Nowadays drums are typically 4 to 8 m in
diameter and 1.20 m to 1.50 m wide. The drum is tightly
sealed to prevent vapour emissions and to direct the air
stream against the direction of drum movement. There
are separate temperature zones to provide fast drying
and to facilitate strip-o from the drum. The drum
surface are usually made from stainless steel or chromium plated steel.
A third type of casting support is a moving plastic lm
with a dened surface structure and special release
properties, see Figure 4. The support lms are generally
PTFE or siliconized PET. The support lm length is
limited, but automated splicing devices are used to avoid
interruptions of the continuous lm casting.
Each of the three solvent cast production methods has
advantages and disadvantages in terms of investment
cost, production speed, production cost, lm quality etc.
The rst preference for the selection of a process is the
feasibility to produce a lm from a specic raw material

e
f
e

A
= manifold of coathanger die
B1/B2 = preland sections

d
a
b
d
e
f

Fig. 5 Caster Lay-out for Solvent Casting

= caster, die, hopper

= drum surface
= drum channel
= drying air
= film take-off

Fig. 3 Cross-section of a Drum Casting Machine

combination with the intended thickness and the other

specied quality requirements.
Caster
This device (caster, spreader, die, hopper) is an important
key element of cast technology. The dope is pumped by a
Fig. 4 Cross-section of a
Support Film Casting Line

special pump through heat exchangers into the spreader.

The function of the spreader is to distribute the liquid
homogeneously over a span of 1 to 2 meters. The
thickness prole of the resulting liquid lm should be
as accurate as possible. The hydrostatic pressure between
the centre and edges of the caster slot has to be
equilibrated by mechanical design as shown in Figure 5
[6]. It is essential to keep the temperature of the liquid in
the caster constant because the resulting viscosity
changes result in inhomogeneous thickness distribution.
Various types of die systems are used, only two examples
are shown in Figure 6. There are many dierent caster
constructions designed for the various processes [7].
In any case, the following principles have to be
considered.

3
2

1
2
3
4
5
6

= support film unwinder

= T-die
= flat bed dryer
= separation point
= support film winder
= product film winder

Fig. 6 Cross-section of dies for Solvent Casting






The rheological situation in governed by laminar

ow
Pressure dierences across the prole have to be
equilibrated
Small internal mechanical defects such as thickness
variations in the slot or changes in surface roughness
can cause lm prole defects
The appearance of transverse lines in the lm
product can be avoided by adjusting geometry,
support speed, viscosity and ow parameters

More detailed evaluation of process parameters for slot

coaters by means of computational uid dynamics is
described elsewhere [8].
Drying process
First drying step
The drying assemblies for casting-on-lm lines, belt
machines and drum machines are constructed quite
dierently to achieve optimum results. The various
Fig. 7 Temperature Balance in
Film Formation Process

methods include indirect heating, heating by radiation

and air-stream drying. They can be separated or
combined in dierent zones to increase the accuracy of
control over lm formation and lm drying at the
support surface. Heated air with no solvent or a low
solvent concentration is blown in, the solvent-loaded air
is exhausted by fans and directed to the solvent recovery
unit.
The treatment of the rst liquid lm in the machine
with solvent loaded air is state-of-the-art for preventing
surface distortions during the lm formation process.
Controlled air ow, e.g. for avoiding vortices is also
important. Maintaining a temperature balance between
the dope, support surface temperature and air temperature during the very rst continuous evaporation of the
solvent out of the liquid lm is one of the most dicult
jobs of the lm casting process, see Figure 7. In addition,
the lm take-o from the support needs precision
adjustment of process conditions. Usually, the lm is
cooled down during the last step to reduce tackiness. If
the tackiness is too low, the lm detaches from the
downside of the belt or drum and the process has to be
stopped immediately. In the rst step, lm formation on
the belt or drum typically yields lms with a relatively
high residual solvent content. In this step, there is only
one open surface. Both open surfaces of the lm are
subsequently dried using more eective drying equipment. The drying process is separated into two steps for a
special reason. Thermoplastic polymer-solvent systems
display dierent diusion regimes. When solvent concentrations are high, the glass transition temperature
falls below the process temperature. As a result, the
diusion coecient of the solvent in the lm is high and
rapid evaporation takes place. Below a certain concentration limit and depending on the chemical nature of the
combination, e.g. near 3 to 6% residual solvent, the glass
transition temperature rises to a temperature higher than

Fig. 8 Drying Conditions Two

Dierent Diusion Regimes

50
solven conc. of film (%)

45

T (film) > Tg

40
T1

35
30
25

T2

T (film) < Tg

20
15
10
5
0
0.01

0.1

10

100

1000

drying time (h)

T2 > T1 drying temperature
Tg = glass transition temperature changes with solvent content

process temperature. The resulting diusion coecient

can be 1000 lower than before, see Figure 8. Therefore,
the process conditions are adjusted to avoid early
solidication of the surface i.e. to avoid a low diusion
coecient and slow drying. Occasionally, chilling is
necessary as a rst process step. Depending on dope type,
temperature and machine construction, the residence
time of lms on a belt or drum is between 0.2 and
20 minutes. Residual solvent at strip-o can vary
between 3% and 40%. The available process condition
options are governed to a very large extent by the type of
material combination. Detailed mathematical modeling
of the lm drying process was investigated by several
groups [9].
Second drying step
As explained before, primary and secondary drying are
generally necessary before and after strip-o in each case.
The lm at the end of the support is in some cases cooled
down by cooling rollers or chilled air. This reduces its
sensitivity to mechanical surface defects and increases its
mechanical strength. Dierent dryer systems exist and a
combination is often used. A oating bed dryer or a
clamp process is used by some companies to avoid
surface scratches resulting from contact with rollers, see
Figure 9. [10]
Ecient drying requires air streams from both sides.
This can be achieved for instance by looping the lm
around a series of polished rollers in drying cabinets
employing jet streams of ltered clean air, see Figure 10.
The exhaust air from the dryers goes to solvent recovery
as well. Heated rollers can be used for special higheciency drying and IR radiators are used sometimes in
the last part of the drying process. Depending on the

length of the drying track, a puller roller system

consisting of several electrically connected and controlled puller motors is required.
At the end of the drying process, edge slitting knifes
and knurling equipment are installed. Knurled edges or,
as an alternative, protective lm are needed to prevent
the surfaces of the single laps from blocking during windup. Web tension control and side edge control for the
product rolls is standard in the lm industry. Even after a
drying process with residual solvent contents of less than
0.5%, the lm still has dierent properties at its air-side
and support-side surfaces, according to the lm formation process. The solvent diusion coecient of a given
polymer-solvent combination is the crucial parameter
governing production speed. Nowadays, the typical
production speed for casting lines is 10 ... 60 m/min, or
in area terms depending on the lm width > 600 to
6000 square meters/h.
In-line coating
It is possible to apply coatings to the lm during the drying
process, but it will not explained in detail here. In-line
coating should be mentioned because it is a standard
process in the photo lm industry and consumes a vast
amount of solvent cast lms. Coating equipment is
integrated into the middle of the drying track. Both
surfaces can then be coated and several layers subsequent
applied. Organic solvent- or water-based coatings are dried
on the lm surface before it comes into contact with the
next roller. Air jets and infrared devices are used to enhance
drying speed and sometimes the coatings require a UV- or
heat-curing step (hard coat, anti-glare coating). Roll
coating or slot coating techniques are used to apply curl
correction, gelatine substrate, antistatic, slip agent, a

Fig. 9 Clamp or Tenter Dryer

1 = film
2 = pin tenter
3 = casting die
4 = support drum
5 = stripping roll
6 = hot air
7 = drying chamber
8 = grooved roll

colored layer, diusion barriers, optically active liquid

crystal layers, magnetically active layers and others.
Solvent recovery and handling
Legislative conditions
Obviously, solvent casting cannot be mastered without
detailed know-how and experience in handling organic

solvents. Some of the most commonly used solvents for

casting purposes are methylene chloride, methanol and
acetone. Use of these solvents is subject to numerous
restrictions. The table of limit concentrations for exposure illustrates German regulations is shown in Table 2.
There are many more regulations governing the construction and operation of casting facilities as well as
discharging. In Germany, for instance, more than 400
laws and regulations on environmental issues and
healthcare have to be taken on board. Extra tight

Fig. 10 Air Flotation Dryer

Roller cabinet

Roller cabinet

Air flotation dryers

Table 2 Environmental, Safety and Occupational Exposure of Solvents

Regulations in Germany
Solvent
Typical use of
solvent

* 8 h- TWA limits
[mg/m3]

** STEL
[mg/m3]

Max. exhaust air

concentration
[mg/m3]

Max. wastewater
concentration [mg/l]

*** LEL * 0.5 [g/l]

Acetone

1200

4800

150

30

260

1040

150

10

36

360

1440

20

0,1

230

Methanol
Methylene
chloride

Solvent for PVDF,

Coating solutions
Solvent for TAC,
coating solutions
Solvent for PC,
PES, PEI, TAC

*8 h-TWA = 8 hours time weighted average

**STEL = Short time exposure limit
***LEL = Lower explosion limit

casings, ttings, seals, double-shell tanks with automatic

leakage monitors, extra retention basins for incidents,
explosion-proof equipment, automatic re detectors and
sprinklers, automatic in-line measurements of exhaust air
from the recovery process, solvent detectors for waste
water etc. are part of the established standards for newly
constructed lines. In several companies, the air in
working zones is monitored continuously, in others it is
monitored specically during critical processes such as
dope lter changes. No more details will be discussed
here on this item because there are many dierences in
legislation, not only between countries, but also between
states and even local authorities.

De-sorption is performed by means of a hot nitrogen

stream or by steam. The charcoal bead has to be dried
and cooled before the start of the next adsorption cycle,
see Figure 12. After steaming out, the solvent-water
mixture is condensed and distilled. If a binary or ternary
solvent was used, a series of columns is needed for
purication. Typical performance data for activated
charcoal absorbers are: 5 tons of activated charcoal can

Recovery and incineration

Table 3 shows a summary of suitable recovery and
decomposition processes for solvents [11].
Adsorption process
The most eective and exible recovery process in terms
of reducing solvent concentrations to very low levels is
the adsorption process using activated charcoal. Other
adsorbents such as silica gels, zeolites and polymer beads
have also been tested [12]. The standard adsorption
process runs discontinuously and alternatively in two or
more columns, see Figure 11.
Table 3 Solvent Recovery and Combustion Optimum Process
Feed Concentration
Indirect Condensation
Adsorption process
Absorption process
Direct condensation
Membrane process
Thermal oxidation
Catalytic oxidation
Bio lter

>50 g/m3
1100 g/m3
150 g/m3
>25 g/m3
>20 g/m3
>10 g/m3
3 ... 10 g/m3
0.23 g/m3

Fig. 11 Solvent Recovery Process by Adsorption

10

Fig. 12 Adsorption / Desorption

Isotherms of Active Carbon

% solvent load on active carbon

De-sorption at 120 C

Adsorption at 30 C

40

adsorption process

heating

30

20

cooling
10
de-sorption process

0
0

0.05

0.1

0.15

0.2

0.25

0.3

partial pressure of solvent

adsorb a dierential load of about 600 kg of methylene

chloride. Depending on volume ow, feed gas concentration and bead diameter, one loading cycle can vary
between 3/4 of an hour and 3 hours. The puried gas
contains only 1 5 ppm solvent and reaches 20 ppm at
the end of the loading process according to the legal
regulations. About 0.8 kg steam of steam is required to
recover 1 kg of solvent i.e. steam consumption is an
important cost factor in solvent recovery by this method.
Other adsorptive substances have been tried, but they are
either ineective or too expensive for organic solvents. A
system of continuous adsorption using a system of
circulating activated charcoal pellets has been put
forward. In practice, however, adsorber charcoal debris
levels were too high, resulting in valve pollution etc. and
in higher adsorber material consumption costs. The
wheel process is another attempt to continuously run
the adsorption process with activated charcoal instead of
using columns.
Absorption process
In the search for other continuously operating recovery
principles, the absorption into liquid carrier was adopted
and plants of this type set up in several sites, diagram in
Figure 13. The most important parameter governing this
process is the partition coecient of a specic solvent to a
specic liquid carrier. The temperature dependency of
this coecient is used to absorb and desorb the solvent in
a similar way to the adsorption process. Unfortunately,
to run the process eectively many solvents need cooling
in the absorption step. This increases recovery costs
substantially. The carrier liquid should be stable over
many years without signicant degradation. Substances
with low vapour pressure and high boiling points are

preferred to permit solvent recovery by a simple stripping

process. For instance diethyleneglycolmethylether was
used in a recovery plant for a mixture of the solvents
ethanol and trichloroethylene [13]. Table 4 shows a
comparison of both recovery methods. Unfortunately,
it is impossible to achieve a very low exhaust air solvent
concentration as legally required for solvents with high
vapour pressures, such as methylene chloride.
Cooling-out
Cooling can be a very eective way of cleaning the
process air, depending on the boiling point of the solvent.
In the case of commonly used solvents, large amounts
of energy have to be consumed to achieve the required
low concentration in clean air. On the other hand,
continuously operating condensers are compact and lowmaintenance. As a result, cooling devices are used to
recover solvents for the make-up of the process air in the
casting line, Figure 14. Given the vapour pressure curve,
the high solvent concentration in air can be reduced to
the equilibrium concentration at a given temperature
with only moderate power consumption.
Incineration thermal or catalytic
These are not really solvent recovery methods so much as
ways of recovering thermal energy [14]. Thermal incineration is generally required for complex mixtures of
solvents if separation by distillation is too expensive. A
similar reason is the use for production lines which use
various solvents at dierent times. The exibility to
switch over to another solvent in a short time cannot be
achieved in the recovery systems discussed before.

11

Solute = solvent for recovery

Solvent = carrier for the absorption process
Fig. 13 Solvent Recovery Process by Absorption
Table 4 Comparison of Adsorption and Absorption for Solvent Recovery Process

Use of energy
Process
Technical experience
Feed concentration
Concentration in cleaned air
Corrosion
Probability of incidents
Purity of recovered solvent

Adsorption (Active Carbon)

Absorption (Liquid)

>10 kW/kg solvent

Discontinuous, many mechanical parts
>80 years
A wide range of concentrations possible
Low, < 20 ppm (for Methylene Chloride)
Corrosive products by catalytic degradation
Medium (active carbon)
Solvent water mixture, degradation products

>6 kW/kg solvent

Continuous, few mechanical parts
>20 years
Mainly for concentrations>20 g/m3
Medium for solvents with low boiling points
Negligible
Low
High purity without additional purication steps

Products and Markets

Principal advantages and drawbacks
of solvent cast lms
The main advantage of solvent cast technology is caused
by the unique process drying a liquid on a surface
without applying further mechanical or thermal stress.
Additionally, dope handling and ltration oer a variety
of specic features for the nal product. Advantages are:





Homogeneous thickness distribution

Highest optical purity, free of gels or specks
Excellent transparency, low haze
Isotropic orientation, low optical retardation, excellent atness




Processing of thermally or mechanically sensitive

components is feasible
Possibility of production of high-temperature resistant lms from non-melting but soluble raw materials

There are constraints on the types of polymer lms for

which solvent casting technology must or cannot be used.
Relatively few materials can be processed into lms by
both methods slot extrusion and solvent casting. In
these cases, a cost-performance comparison decides.
Very thin lms cannot be produced by extrusion without
stretching, very thick lms are very costly to produce by
solvent casting and lamination. In general, solvent-cast
products are more expensive than extruded lm to
manufacture for several reasons:

12

Fig. 14 Internal Solvent

Recovery by Cooling

4
3
5

1 = dope mixer
2 = holding tank
3 = de-aeration device
4 = condenser
5 = solvent recovery, schematic

Slow production speed depending on a slow solvent

diusion process
Extra energy costs of solvent recovery
Investments in facilities for handling solvents and
dope solutions

The market is rapidly declining since 2002 because of the

erce competition of digital photography.

On the other hand, the performance and, more specifically, the high quality of solvent cast lms cannot be
achieved using other processes. This will described in the
next chapter.

Optical polarizers are based on polyvinylalcohol lms

cast from an aqueous solution. This lm is stretched and
doped with iodine or organic dyes to provide the
polarizing function. The polyvinylalcohol polarizing
layer is usually protected against mechanical and other
environmental eects by two cellulose triacetate lms
with highest optical properties and very low birefringence, see Figure 15 [5]. Each LC display needs two
polarizers by virtue of the physical principles governing
the electro-optical eect of the liquid crystals.
The fastest-growing area of solvent cast lms with
more than 20% growth per year is the production of
optical cellulose triacetate lm for manufacturing polarizers for LC displays. The quality requirements are much




Examples for solvent cast films

Photographic application
The largest areas of solvent cast lms are produced for
photographic use. About  300 million square meters of
cellulose triacetate lm base are used every year for
35 mm amateur lms, movie lms and other lm types.

LCD applications

TA C protection film, 80mic

PVA (Polyvinylalcohol) polarizing film, 20mic
Adhesive

TA C protection film, 80mic

Wide angle view or retardation film, 70 mic
Release liner

LC Cell Side
Fig. 15 Cross-section of a LCD polarizer

13

higher than for photographic TAC lm base. The

actual consumption in 2004 was about 200 Mio square
meters / year. A recent application is the use of LC
displays for TVs (up to 62 inch screen). This will rapidly
increase the use of cellulose triacetate based solvent cast
lm in the near future.
Polycarbonate is used for several specialty lms, some
of them designed for optical purposes. Compensation or
retardation lm is required in STN LCD displays to
correct the color appearance, increase contrast and
viewing angle [15]. Recently, a new type of cyclic olenic
polymer ARTON R was introduced for the application
wide view angle enhancement in TFT LCD [16]. The
ARTON R lm is produced by solvent casting in volumes
of several million square meters per year [17]. It allows a
viewing angle of more than 170 and is mainly used in
LCD TV sets.
Other optical applications
Cellulose diacetate, soluble in acetone, is converted to
lms by means of solvent coating mainly in thicknesses
between 14 and 200 microns. Since about 1950, big
volumes have been used for applications such as print
lamination, graphic arts, windows in food stu boxes,
photographical sleeves, googles and visors. The advantages of this lm type are high gloss levels, excellent
transparency and a good balance between moisture
resistance and water permeability. That makes it an
ideal lm especially for the combination together with
paper or carton. The actual consumption of the
cellulose diacetate lms is about 4000 to 4500 tons/
year [18].
Another optical application is a solvent cast lm made
from polycarbonate for the use in a new type of optical
storage media blue ray disc [19].
Electrical and Electronic applications
Other advantages of cast lm technology are important
for electrical and electronic applications. Electrical
properties that are stable at high temperatures over the
long term can only be achieved with polymers with high
or no melting temperatures. Processing of highly puried
and ltered polymers with high glass transition temperatures, high bulk resistivity and a low dissipation factor is
possible. It is often not feasible to produce these lms
using thermoplastic manufacturing methods. In some
cases, a soluble polymer such as poly (amide carboxylic)
is cast from solutions in dimethylacetamide to form a
lm which is subsequently cross-linked with acetic
anhydride during the casting process. Typical products
are base materials for exible printed circuits, insulation
lms, wrappings, capacitors etc.

Polymers such as polycarbonates, polyimides, etc. are

used for these purposes. Consumption of this type of lm
is increasing with the growth of the electronic industry
and the development of new, more sophisticated electronic devices. The sales forecast for just one type of
polyimide lm (KAPTON R) for 2004 is about 3000 tons
with high added value.
High-temperature applications
Some of the high-temperature applications are identical
to the list shown above for electrical / electronic use.
Depending on the temperature requirements and the
chemical composition of the polymer, cast lm
techniques can be used for release lms. Polyimides,
cellulose triacetate and others are the typical raw
materials.
Another emerging area is the application of hightemperature resistive lms for LCDs, as already mentioned, and as substrate materials for OLED displays
[20]. Feasible trial lms have been made on the basis of
polyether sulfone, polycarbonate, cyclic polyolens,
polyarylates and polyimides.
Diverse Applications
There are various lm applications which require the
specic advantages of the solvent cast lm process:





Very high load of ller or functional compounds

Homogeneous thickness distribution
Gauges of 100 mic or below
Low shrinkage

The products have a variety of specic properties:

High electrical or thermal conductivity, high magnetic
coercivity, conductivity of protons for fuel cell membranes, substrate for diagnostic lms with a dened
optical remission, highly lled lms for tamper-proof
labels, weather-proof labels etc.
Acoustic membranes produced from solvent cast lms
have to possess:




Very thin gauges and a matt surface

Isotropic mechanical properties before and after
thermoforming
Long-term stability under mechanical stress

These membranes are used in normal-sized and miniature loudspeakers, e.g. for mobile phones. Typical raw
materials are polycarbonate and polyarylate [21].
To achieve a controlled pore structure, another
inherent advantage of solvent casting is used [22]:


Solubility, partial solubility in solvents and in-line

precipitation and extraction process

14

Products based on proprietary processes have been used

for diuresis membranes, desalination membranes, waste
water purication and other membrane processes for
many years. Cellulose derivates, polysulfones and polyimides have been used for these purposes.

Conclusion
The oldest technology for the production of thin polymer
lms is nowadays used for niche products with high
quality requirements such as photographical lm base,
exible printed circuits, high-temperature resistive lms,
loudspeaker membranes etc. In recent years, mainly new
optical applications needed new amorphous lms with

highest clarity and specic optical birefringence properties. In most cases, these amorphous lms are not easily
accessible by Rulands structural investigation methods,
because the absence of microdomains or crystallinity is
one of the assumptions to provide good solubility in
organic solvents and in particular a perfect glass-like
appearance after the lm formation process. The future
of solvent cast technology will be closely linked to the
need of optical lms by the emerging liquid crystal
display industry or other new optical applications which
require polymer lms with outstanding properties.
Acknowledgement I am most honoured to have the opportunity to
proer my profound gratitude to Professor Ruland, who was able,
during my thesis work, to explicate the mysteries of the reciprocal
room ... even to a chemist.

References
1. Collins D (1990) The story of Kodak.
HN Abrams Inc, New York
2. Steven, Leerts (1896) USP 573928
3. Couzens EG (1968) A short history of
the lm casting process and its products. Bexford Ltd, Essex
4. Adelstein PZ et al (1972) Manufacture
and physical properties of lm. Paper
and plates. 127 , Neblettes handbook
of photography and reprography
5. Sata H, Murayama M, Shimamoto S
(2004) Properties and application of
cellulose triacetate lm. p 323333,
Macromol. Symp. 208 (2004)
6. Lippert HG (1987) Polymers, lamination and coatings conference. 193
7. Durst F et al (1989) Coating, 434

8. Muller C et al (1997) Sensitivity analysis of slot coaters, p 115, University

of Erlangen-Nurnberg, von Karman
Institute for uid dynamics. Lecture
series 19976
9. Alleborn et al (1997) Analysis of lm
drying. Lecture series 199706, University Erlangen-Nurnberg: Thin liquid
and coating processes
10. Takeda R et al (1992) USP 5 152 947
Fuji Photolm
11. Nitsche M (1991) Technische Mitteilungen 84: 72
12. Mathews W (1991) Technische Mitteilungen 84: 78
13. Lerch H (1991)Technische Mitteilungen 84: 87
14. Calowitz O (1991) Technische Mitteilungen 84: 94

15. Nagoshi T (1998) Optical lms and

methods for producing the same, EP
0992331 A1
16. Fukuda T Kagaku kogaku 61, 405407
17. EP 1342 745 A1
18. Law PW, Longdon A, Willins GG
(2004) Macromol. Symp. 208: 293323
19. EP 1 195 758 A
20. Angiolini S (2002) Eurodisplay 22, Le
Club Visu-SID France p 907910
21. EP 0306905
22. Melzner D (2002) Funktionspolymere
fur Systemlosungen, GDCh Fachgruppe Makromolekulare Chemie,
Vortragstagung Darmstadt:59