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Preparation Of Charge Transport Layer ( CTL )

The preparation of Charge Transport Layers for use in xerographic films is generally
considered tricky for the novice, fortunately the problem of incomplete dissolution of the
main binding constituent ( polycarbonate ) can be completely eliminated through proper
mixing techniques.
The following formulation example is given to illustrate the technique and of course
substitutions in specific constituents may be made for given application requirements. In
the example, all of the materials percentages are by weight.

Typical CTL Composition

Constituent Percentage
( rounded )

Merlon MPG-3408 polycarbonate ( Mobay Chemical Company ) 9.40


Binder

Vitel PE-200 polyester ( Goodyear Tire and Rubber Company ) 0.47


Plasticization / Adhesion

DEH: 1,1 diphenyl hydrazone of para diethylamino benzaldehyde ( Aldrich ) 7.51


Hole Transport Molecule

Savinyl Yellow / Acetosol Yellow 5GLS ( Sandoz ? ) 0.038


UV Filter / Room Light Fatigue

Tetrahydrofuran Coating Solvent 82.63

DC-200 silicone oil - 10 cs viscosity ( Dow Corning ) * 1 - 2 drops /


liter
Wetting / Leveling Agent

Optional Solvent System:

Tetrahydrofuran 74.8 - 78.84

Cyclohexanone 4.15 - 13.2

The above CTL is typically coated at 16 - 22 um thickness on both flex webs and drums.
The composition is generally filtered prior to use through a Pall / Trinity, Seal Kleen
filter ( SLK 2001 BNP ) which is typically rated at 1.2 - 1.5 um. The pressure filtration
is driven by nitrogen, this is to prevent oxidation of the transport molecule.

The optional binary solvent system containing the co-solvent Cyclohexanone has
application in several areas. This system is preferred where solution stability and longer

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“ pot lives “ are desired, this is due to the fact that Cyclohexanone is a true solvent for
polycarbonate, the typical concentration is 5 - 15 % by weight.
This co-solvent system also aids in the prevention of “ cold shock “ which is signified
by a hazed or cloudy appearance of the coating upon drying. This is due to the
incorporation of water into the film caused by a solvent evaporation rate that is too
aggressive during those frustrating periods of high ambient humidity. This solvent
system slows down the evaporation rate such that condensation of water on the surface of
the coated article is greatly reduced or eliminated completely.
Blistering of the CTL is often encountered upon curing due to elevated temperatures in
the cure ovens especially with thicker coatings. One must be able to cure the CTL in a
reasonably short period of time to increase process efficiency, hence oven temperatures
are usually increased to compensate for the increased speed. This can result in skinning
of the coating composition which leads to blistering due to entrapment of solvent further
down into the bulk of the coating layer which is trying to escape the coating.
Turning down the oven temperatures can result in incomplete cure of the coating and
will require longer process cycle times, this situation is counter to the goals of increasing
the process capacity and utilization.. It is possible that a balance between process speeds
and the elimination of blistering can be achieved by this composition. The high boiling
and leveling characteristics of this solvent system have been found to eliminate both the “
cold shock “ and blistering tendencies of the CTL composition while conferring stability
to the coating solution with respect to solution age.
The down side to the use of the binary solvent system for drums is related to consistent
coating thickness along the length of the drum. Dip coating is a true meniscus technique
and coating thickness is dominated by the percent solids ( viscosity ) of the CTL coating
solution and the withdrawal speed of the drum during the coating cycle. This relationship
is depicted in figure A for a given coating thickness.

Figure A

Percent Solids

Withdrawal Speed

From this relationship it can be seen that for a given desired coating thickness, one must
either modify the percent solids of the coating solution or adjust the withdrawal speed of
the coated drum. As Ep technology is materials limited ( few workable materials ), it is
not generally possible to increase viscosity of the coating solution by additions of some
high molecular weight additives to obtain greater coating thickness and vice versa.

The optional binary co-solvent system tends to exhibit “ sagging “ of the coating during
the cure cycle due to the high boiling nature of the Cyclohexanone. This is the result of
greater solution mobility down the length of the drum during the initial phase of the cure
cycle at operational oven temperatures.

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This tendency has not been a major problem due to the capabilities of the dip head
control system. The strategy thus far has been to live with this “ sagging “ tendency and
to compensate for this characteristic as seen in figure B.

Figure B

Withdrawal Speed

Drum Length

The technique employed is to program the dip head controller to withdraw the drum at a
higher speed initially and then to “ ramp “ down the speed as the drum is withdrawn
from the coating solution. The result has been a fairly consistent coating thickness along
the length of the drum.

Technique For Mixing CTL

A) Charge mixing vessel ( tank ) with solvent( s ), start air driven mixer at high speed.
Create as much shear as possible! 15 to 20 liter round bottom glass or stainless steel
reactors ( wide mouth ) work nicely for lab scale batches.

B) Add DC-200 at a concentration of 1 drop / liter. Add the wetting agent to the
solvent.

C) Add polyester, this material will take the longest time to dissolve, go to step D.

D) Flake ( salt ) the polycarbonate into the solvent, many smaller additions are required.
Add polycarbonate until the solution turns cloudy, allow to mix until the solution
clears and then make another addition. Continue to make additions until all of the
polymer is in solution. Cover the mouth of the vessel between additions to limit
solvent loss due to evaporation.

E) Add Savinyl Yellow ( Acetosol 5GLS ) and DEH last. Allow CTL to mix until all of
the components are in solution.

F) Transfer the CTL to a pressure vessel for filtration.

The trick to making CTL is in getting the polycarbonate to dissolve in a timely manner
to completion. If the material is added all at once, the polycarbonate will “ ball up “ and
may never dissolve in the solvent. A highly cloudy solution appearance with “ chunks “
of polymer floating around in it might as well be thrown away as it will not likely be
useable for days if at all!

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The technique of making several small additions with mixing will result in the polymer
going into solution in a short period of time. This will also produce a solution without
large numbers of polymer aggregates / gels that will require significant filtration.
Never add the wetting agent ( DC-200 ) directly to the mixing vessel as it will adhere to
the bottom of the vessel without ever wetting out the polycarbonate particles, only add
the DC-200 to the solvent system already in the vessel. DC-200 is very active and an
addition of 1 drop will be effective up 3.5 liters of CTL. At the opposite end of the
spectrum, a concentration of > 5 drops / liter will likely result in de-wetting and the
characteristic “ fish eyes “ in the resulting CTL coating. DC-200 lowers the surface
energy of the CTL, this aids in removal of toner during the transfer / cleaning cycles and
reduces CTL wear due to abrasion. The 10 and 100 cs viscosities are preferred.
In the case of this composition the yellow dye and the transport molecule are added to
the solution at the same time and last due to their high solubility. This is to prevent any
confusion as to whether the transport molecule was ever added to the batch. This
situation has arisen in the past and it is difficult to catch the mistake until a large number
of drums have been processed and then had to be rejected due to no discharge.
On the subject of yellow dye, the purpose is to act as a UV filter in the transport layer to
reduce room light fatigue. This is the same reason that photoconductors are processed in
areas featuring yellow lights or filters. The concept is effective up to a point, a content of
0.2 % based on the weight of the solids will protect the photoconductor from room light
fatigue for up to 30 minutes exposure. Beyond this concentration, the yellow dye acts as
a diluent negatively effecting mobility. The use of the dye should never be viewed as a
substitute for storing finished photoconductors in the dark. Finished pc’s ( those coated
with CTL ) should always be stored under or behind dense black curtains or in black
boxes to eliminate accidental exposure to UV / room light.
In the area of filtration, it should be noted that the finished CTL batch will have a
slightly cloudy appearance. This is due to micro crystalline polycarbonate particles. The
cloudy haze ( opacity / turbidity ) is an indication of light scattering due to these
particles. Nepholometery is a good process control tool that will quantify the cloudiness
that one may see with the human eye. The above CTL has been processed at the ultra
filtration level ( 0.2 um ) and the resulting solution was absolutely clear! Analysis of this
solution indicated a shift in the constituents with the polycarbonate being lean and the
DEH enriched, this would indicate stripping of the polycarbonate and gives some insight
into the molecular size of the polymer. It is generally not necessary to go to this extreme
with the CTL, a 1.2 - 1.5 um final filter is adequate for most coating applications.
Barrier Layer, Sub Layer and Charge Generation Layers are all pressure filtered at the
0.2um ( SLK 2001 NRP ) level for removal of solution borne contaminants. These
coating solutions tend to be of very low viscosity and the filtration is accomplished at a
very rapid rate where as the CTL is a much higher viscosity and is generally processed at
a slower rate near the coat head entrance. Air bubbles in the filtrate are to be avoided at
all times.
Printers operating in the DAD mode are more susceptible to print defects than printers
operating in the CAD mode and of course print defects are a multifaceted topic. Insoluble
particles of polycarbonate or other contaminants in the CTL ( or other layers ) have been
a cause for print defects, hence any solution borne contaminates due to incomplete
mixing of solutions must be eliminated prior to coating.

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Solution borne contaminates may also be in the form of very small conductive “ ionic “
particulates that may pass through the filter, try adding a small quantity of finely ground
iron oxide to the coating solution and observe the result.
Air borne contaminates will generally be viewed as debris in the coating and must be
eliminated through attention to detail in the clean room and on the drum introduction side
of the process. Class 1000 clean rooms are the minimum requirement for acceptable
quality yield, the closer one comes to a class 100 environment the better. It is advisable
that the coat tanks be fitted with shutters or some other type of covers so that the coat
tanks can be protected from introduction of debris between coating cycles and during
down times. It should be recognized the photoconductors are essentially equivalent to
semiconductors and in both cases a single small speck of dust incorporated into one of
the layers can destroy both devices.
Coating defects such as blisters, drag marks, runs, coating voids and the like must also
be avoided. Air bubbles in the coat tank will generally find their way to the surface of the
article being coated. This will result in uneven coating thickness locally in the area
contacted by the bubble especially when coating CTL. The result will likely be a stripe
down the length of the drum, usually due to lower local charge in this region. It was
found experimentally that a perturbation in the charge field of as little as 50 volts could
be developed consistently.
Defects are also associated with the anodized aluminum drum itself. Aside from the
every day run of the mill contamination that must be eliminated at the cleaning station
there are stress cracks in the anodized surface, ridges and gouges from poor extruding /
machining, bumps on the surface and splotchy defects due to disruption of the anodized
surface caused by poor rinsing after the nickel acetate bath. Many of these defects are
seen only upon cycling as a result of fatigue, both Maxcore and Floturn drums exhibit
these features however Floturn’s quality appears to be slightly higher.
A small dot defect on a printed document, especially a financial document, in the
wrong place can wreck havoc with an account. Since it will never be known what type of
environment a printer may be used in, such print defects are totally unacceptable. Clean
rooms at class 1000 ( or better ), immaculately clean parts entering the process, filtration
and attention to detail are all required in order to produce the highest acceptable quality
photoconductors for today’s marketplace.