U.S. patent number 3,847,606 [Application Number 05/339,084] was granted by the patent office on 1974-11-12 for protecting photoconductor surfaces.
This patent grant is currently assigned to Pitney-Bowes, Inc.. Invention is credited to Leon N. Hecht, Jr., Leon J. Schwartz, Gerald M. Spiegel, Jr..
United States Patent |
3,847,606 |
Schwartz , et al. |
November 12, 1974 |
PROTECTING PHOTOCONDUCTOR SURFACES
Abstract
A method and composition for protecting the surface of
photoconductors which are employed in electrophotography and
xerography which comprises coating the photoconductor surface with
a thin uniform layer of a polyurethane material to protect and
stabilize the photoconductive properties of the photoconductor. The
polyurethane layer should have a charge acceptance of at least
1,000 volts.
Inventors: |
Schwartz; Leon J. (Monsey,
NY), Spiegel, Jr.; Gerald M. (Bridgeport, CT), Hecht,
Jr.; Leon N. (Stamford, CT) |
Assignee: |
Pitney-Bowes, Inc. (Stamford,
CT)
|
Family
ID: |
23327422 |
Appl.
No.: |
05/339,084 |
Filed: |
March 8, 1973 |
Current U.S.
Class: |
430/67; 430/88;
430/94 |
Current CPC
Class: |
G03G
5/14769 (20130101) |
Current International
Class: |
G03G
5/147 (20060101); G03g 005/04 () |
Field of
Search: |
;96/1,1.5,1.8
;117/161KP |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Klein; David
Assistant Examiner: Goodrow; John L.
Attorney, Agent or Firm: Soltow, Jr.; William D. Scribner;
Albert W. Vrahotes; Peter
Claims
What is claimed is:
1. A photoconductive insulating composition comprising a layer of
photoconductive insulating material having a mixture of cadmium
sulfoselenide and photoconductive zinc oxide for electrostatic
imaging and a thin, uniform top coating of polyurethane having a
thickness from 0.02 to 0.1 mil closely bonded to and substantially
over the entire surface of said photoconductive insulating
material.
2. The composition defined in claim 1 wherein the polyurethane
coating has a charge acceptance of at least 1,000 volts/mil of
thickness.
3. The composition defined in claim 1 wherein the polyurethane
coating has a charge acceptance of at least 1,500 volts/mil of
thickness.
4. The protective top coating defined in claim 1 wherein said
polyurethane is an aliphatic type urethane applied from a solvent
taken from the group consisting of isopropanol, cellosolve acetate
and methylethyl ketone.
5. A xerographic plate comprising
A. an electrically conductive substrate;
B. a photoconductive electrically insulating composition adhered to
said substrate, said composition comprising
1. a binder and
2. a pigment comprising a mixture of cadmium sulfo-selenide and
photoconductive zinc oxide,
a. wherein the proportion of cadmium sulfo-selenide is 20 percent
to 70 percent and the proportion of zinc oxide is 30 percent to 80
percent by weight of total pigment; and
C. a thin uniform top coating of polyurethane is adhered to said
composition,
1. said polyurethane coating having a charge acceptance of at least
1000 volts per mil of thickness.
6. The xerographic plate defined in claim 5 wherein said binder is
polyurethane.
7. The xerographic plate defined in claim 5 wherein said
polyurethane coating has a thickness of from 0.02 to 0.1 mil.
8. The xerographic plate defined in claim 5 wherein the mole
fraction ratio of selenium to sulfur in said cadmium sulfo-selenide
is from 0.05 to 0.7.
Description
BACKGROUND OF THE INVENTION
This invention relates to xerography and electrophotography and
more particularly to a method and composition for protecting and
stabilizing the photoconductive insulating materials employed in
connection therewith.
In the art of xerography, it is usual to form an electrostatic
latent image on a member or plate which comprises a substantially
electrically conductive backing member such as, for example, a
paper or metallic member having a photoconductive insulating
material applied to the surface thereof. It has previously been
found that a suitable electrostatic image forming member for
xerographic purposes is an electrically conductive backing member,
for example, metal, which may be employed in the form of a sheet,
drum or belt, having applied to the surface thereof, a
photoconductive material, for example, selenium, inorganic
materials, such as cadmium sulfo-selenide, cadmium sulfide, zinc
oxide and mixtures thereof; organic materials such as complexed
poly-N-vinyl carbazole, and other like photoconductive materials
useful for such purpose. These electrostatic image forming members
are characterized by being capable of receiving electrostatic
charge and selectively dissipating such charge when exposed to a
light pattern.
In the practice of the art of xerography, employing such
electrostatic image forming members as hereinabove described, it
has been found that said electrostatic image forming members suffer
from various disadvantages. It has been found that handling of the
light sensitive surface has a tendency to cause contamination
thereof and the subsequent image reproduction capabilities of the
member are adversely affected. In addition, the xerographic process
is inherently abrasive to the surface of the image forming members
employed which results in a wearing out of the photoconductive
surface requiring frequent replacement of the image forming
member.
Specifically, although there are some materials which are known to
possess satisfactory photoconductive properties, they have not
heretofore been capable of use in xerographic processes, and
especially xerographic copying machines because of their high
susceptibility to the abrasive wear encountered in the operation of
such machines. For example, U.S. Pat. No. 3,658,523 discloses a
cadmium sulfo-selenide/zinc oxide photo-conductor composition which
cannot be employed in xerographic copying machines for this
reason.
Further, it has been found that superior xerographic results are
obtained when a magnetic brush toning process is employed for image
reproduction. However, this magnetic brush toner process is highly
abrasive to the photoconductive surface of the image forming member
resulting in xerographic reproductions of inferior quality and
frequent replacement of the image forming member.
Attempts have been made to protect the surface of photoconductors,
all with limited success. For example, overcoating of
photoconductors has been suggested in Dessauer et al, U.S. Pat. No.
2,901,348; Deubner, U.S. Pat. No. 2,860,048; Kensella, U.S. Pat.
No. 3,146,145 and Petruzella, U.S. Pat. No. 3,617,265. These prior
art attempts have had limited success for a number of reasons.
Initially, they are not universally applicable to the variety of
photoconductive materials with which they are employed, either
because of incompatability of the materials in their physical or
chemical relationship or because inapplicability of the process
employed in obtaining the desired protected photoconductor member.
One manifestation of this latter disadvantage of the prior art
teachings can be seen from a study of the process disclosed in U.S.
Pat. No. 3,617,265 wherein a heating-quenching process is employed
in preparing the desired protected photoconductor member. The
application of such a process to various photoconductive materials
having binders of organic resin materials, a widely employed
practice, will result in a basic and detrimental alteration of the
photoconductive member and its photoconductive properties.
We have now discovered a method of producing an electrostatic image
forming member useful in the practice of xerography which overcomes
the problems heretofore experienced with prior art image forming
members which were susceptible to surface abrasion and
contamination. More particularly, we have discovered a method
whereby the abrasion susceptible surface of the photoconductive
material employed in the electrostatic image forming member of the
xerographic process may be protected which also tends to stabilize
the photoconductive properties thereof.
Accordingly, it is an object of the invention to provide a
composition useful in xerography wherein the photoconductive
insulating material is protected from mechanical wear and
abrasion.
It is a further object of the invention to provide a composition of
the above character which helps to stabilize the electrical
properties of the photoconductive insulating material.
The invention accordingly comprises a composition of matter
possessing the characteristics, properties, and the relation of
components which will be exemplified in the composition hereinafter
described, and the scope of the invention will be indicated in the
claims.
SUMMARY OF THE INVENTION
In general, our invention comprises the application to the
photoconductive surface of an electrostatic image forming member,
of a thin uniform coating of polyurethane to provide positive
protection against abrasion and contamination. Specifically, we
have found that the photoconductive surface of electrostatic image
forming members can be protected from abrasion and contamination by
the application thereto of a thin, uniform coating of a
polyurethane.
The polyurethane coating which may be satisfactorily employed in
the practice of this invention must have a very high resistance to
abrasion. In addition, the polyurethane must have low surface
leakage properties as indicated by a high dielectric strength and
surface resistance, so that the applied electrical charges will not
be dissipated by bypassing of the underlying photoconductive
material. The total surface leakage of the polyurethanes which are
useful in the practice of this invention may be determined in the
same manner as is done for photoconductors, i.e., a thin coating of
the polyurethane, about 1 mil or less, is tested for charge
acceptance. We have found that when the polyurethane is tested by
being charged in a Victoreen Electrostatic Paper Analyzer the
polyurethane must accept a charge equivalent to at least 1,000
volts/mil of thickness and preferably at least 1,500 volts/mil, to
yield satisfactory results hereunder.
DETAILED DESCRIPTION OF THE INVENTION
The polyurethane coating must be inert to the photoconductive
material upon which it is to be applied and must have good adhesion
properties which will permit its permanent bonding to the
photoconductive surface on which it is applied. The adhesion
properties of the polyurethane must provide a uniform coating and
help prevent air pockets or other surface irregularities which
could interfere with the photoconductive properties of the image
forming member. In addition to the foregoing, the polyurethane
coating must have fast air drying properties to permit facile
coating thereof on the photoconductive surface. In the practice of
this invention we have found that a polyurethane capable of being
cured by solvent evaporation provides satisfactory results.
The electrically conductive backing member which may be employed in
the electrostatic latent image forming member useful in the
practice of the instant invention may be comprised of any material
that has been previously found to be satisfactory in the practice
of xerography. Included among the electrically conductive materials
which may be employed in the practice of this invention are metals,
for example, aluminum or brass, conductive paper, graphitized
Mylar, metallized Mylar and other like material.
The photoconductive insulating materials which may be
satisfactorily employed in the practice of this invention are those
photoconductive materials which have heretofore been so employed in
the practice of xerography and which may be satisfactorily applied
on the electrically conductive backing materials. Among the
photoconductive materials which may be employed in the practice of
the instant invention are such materials as selenium, cadmium
sulfo-selenide, cadmium sulfide, zinc oxide, poly-N-vinyl carbazole
and other like materials. In particular, we have found that a
mixture of cadmium sulfo-selenide/zinc oxide is both protected and
electrically stabilized by a thin, uniform coating of
polyurethane.
The polyurethane protective coating employed in the practice of
this invention must have the physical properties set forth
hereinabove. In addition, we have found that satisfactory results
are obtained when the polyurethane coating employed is possessed of
a charge acceptance of at least 1,000 volts/mil of thickness. In
the preferred practice of the instant invention, we have found that
most satisfactory results are obtained when a polyurethane having a
charge acceptance of at least 1,500 volts/mil is employed. The
successful practice of this invention is dependent upon the
characteristics and properties of the polyurethane employed and
although many polyurethanes were tested it was unexpectedly found
that only the polyurethanes possessing the specific properties set
forth hereinabove provided satisfactory results.
The polyurethane protective coating must be applied to the
photoconductive surface in such a manner as to avoid adversely
affecting the photoconductive properties thereof. We have found
that the thickness of the polyurethane coating must be controlled
to avoid masking the photoconductive response to the underlying
photoconductive material, while at the same time providing a
coating which is thick enough to provide the required protection.
We have found that satisfactory results are obtained when the
coating is applied in a uniform thickness of from about 0.02 to
about 0.1 mils; and preferably when the coating was applied
uniformly in a thickness of from about 0.04 to about 0.08 mils.
The polyurethane coating may be applied in any manner which is
known and convenient to the skilled worker, for example, spraying,
painting, Mayer rod, doctor blade or reverse roller applicators,
which will provide a uniform coating of the polyurethane in the
required thickness. In addition, care must be exercised in the use
of solvents employed in the application of the polyurethane coating
to the photoconductive surface so as to avoid interaction of the
solvents with the underlying photoconductive materials or binders
which may have been employed in connection therewith. Satisfactory
solvents which we have found to be employable in connection with
the polyurethane coating material of this invention include such
solvents as isopropanol, cellosolve acetate and methyl ethyl
ketone, although other solvents may be employed as may be
determined by the worker skilled in the art.
The effects of mechanical wear and burnishing have been found to be
particularly pronounced with the use of a mixed pigment
photoconductor system of cadmium sulfo-selenide and photoconductive
zinc oxide. As set forth in copending application Ser. No. 134,730
and assigned to the assignee of this application, the
photoconductor composition should comprise a binder having a mixed
pigment therein of from 20 percent to 70 percent of cadmium
sulfo-selenide and from 30 percent to 80 percent zinc oxide by
weight of total pigment. The mole fraction ratio of selenium to
selenium plus sulfur in the cadmium sulfo-selenide should be from
0.05 to 0.7 e.g. where n equals the number of atoms of sulfur and
selenium the ratio (n(Se)/n(S)+n(Se)) is from 0.05 to 0.7.
When a photoconductive insulating composition of cadmium
sulfo-selenide/zinc oxide is used in a xerographic machine without
a top coating there are substantial changes in the electrical
properties of the photoconductor which reduce its useful life below
commercially acceptable levels. With a thin top coating of a
polyurethane having a charge acceptance of at least 1,000 volts per
mil of thickness, however, the photoconductor is commercially
usable.
Table A shows the necessity for particularly protecting the surface
of a cadmium sulfo-selenide/zinc oxide photoconductor from
burnishing. The effects of burnishing were simulated by rubbing the
surfaces with cotton.
Table A indicates that the mixed CdSSe/ZnO photoconductor shows a
significant reduction in acceptance voltage as compared to either
of the constituents when burnished.
TABLE A ______________________________________ Acceptance Voltage
Range (Volts) ______________________________________ Sample Before
After Burnishing Burnishing ______________________________________
CdSSe 720 - 790 640 - 700 ZnO 195 - 270 240 - 255 CdSSe/ZnO mixture
610 - 640 160 - 195 ______________________________________
It is indicated from the above data that the CdSSe and ZnO
particles interact when the surface is abraded.
Table B below illustrates the effects of changing the pigment to
binder ratio (P/B) and CdSSe/ZnO ratio.
TABLE B ______________________________________ Fraction of
Acceptance Voltage Remaining After Burnishing
______________________________________ CdSSe/ZnO P/B = 3:1 P/B =
6:1 P/B = 9:1 ______________________________________ 100/0 0.85
0.91 0.91 75/25 0.79 0.83 0.86 50/50 0.85 0.74 0.72 25/75 0.84 0.50
0.43 10/90 0.92 0.69 0.45
______________________________________
Table C below illustrates the mechanism of burnishing by simulating
particle interaction by crushing the dry pigment powders before
formulating.
TABLE C
__________________________________________________________________________
Acceptance Voltage Speed Range Sample Range (Volts) (fcs)
__________________________________________________________________________
CdSSe 625 - 720 0.24 - 0.32 Crushed CdSSe 615 - 630 0.33 - 0.43
CdSSe + ZnO 575 - 580 0.13 - 0.19 Crushed CdSSe + ZnO 590 - 630
0.19 - 0.26 CdSSe + Crushed ZnO 510 - 555 0.10 - 0.17 Crushed CdSSe
+ Crushed ZnO 485 - 540 0.16 - 0.27 CdSSe and ZnO Crushed Together
325 - 340 0.07 - 0.12
__________________________________________________________________________
It is indicated from Table C that simple mechanical action alone on
the CdSSe does not account for the significant differences
observed, as is the case when the much harder ZnO particles abrade
the surface of the CdSSe particles in the mixed pigment system.
Lubricants such as diphenylamine and clay added to the mixture have
somewhat helped resistance to burnishing by reducing the
interaction of the particles, but top coating with a thin layer of
polyurethane provides more effective protection. In the above
example there was no evidence of increased dark decay as a result
of crushing. This is very evident in burnished coatings and
probably operates by electrostatic charge injection into the binder
surface as a result of friction. A thin uniform top coating of
polyurethane in accordance with the present invention provides
positive protection against such effects.
This invention is illustrated by the following examples.
EXAMPLE I
A polyurethane resin having a charge acceptance of in excess of
1,500 volts/mil of thickness (commercially available from Cargill
Co. as a 30 percent solution under the designation
"Cargill-X-1513-30" an aliphatic type urethane having a molecular
weight of from 23,000 to 25,000) was applied to the surface of a
cadmium sulfo-selenide/zinc oxide mixed pigment photoconductor in
different thicknesses of from 0.04 to 0.08 mils by diluting the
polyurethane to various solid concentrations before coating. The
higher the percentage of solids, the thicker the coating. The
control had no top coating at all. The respective photoconductor
properties were measured by employment of a modified Victoreen
Electrostatic Paper Analyzer and the results thereof are set forth
in Table D below:
TABLE D
__________________________________________________________________________
Polyurethane diluted to: Control 10% solids 20% solids 25% solids
Charge Acceptance (Volts) 1st charge 910 960 1010 1170 2nd charge
845 880 960 1030 Dark Decay (max) 60 35 50 45 (volts/sec) Speed, t
1/2 0.07 0.10 0.12 0.14 (fcs) (avg.) Exposure to 60 V. 0.21 0.20
0.33 2.00 (fcs) (avg.)
__________________________________________________________________________
The materials of Table D were then subjected to 2500 cycles of
simulated magnetic brush burnishing and were again tested producing
the results set forth in Table B below.
TABLE E ______________________________________ Polyurethane
diluted: Control 10% Solids 20% Solids Charge Acceptance (Volts)
1st charge 635 900 970 2nd charge 290 890 970 Dark decay (max.) 100
110 60 (volts/sec) Speed, t 1/2 .09 .10 .11 (fcs) (avg.) Exposure
to 60 V. .16 .17 .24 (fcs) (avg.)
______________________________________
EXAMPLE II
A photoconductive test belt was made using the following
formulation for the photoconductor composition:
Pigments
90 gms, CdSSe (Dark Red pigment available from Ferro Corp.
containing a Se/S+Se mole fraction ratio of 0.36
270 gms, ZnO (Photox 801 from New Jersey Zinc Co.)
Binder
133.4 gms 45 percent polyurethane (Estane 5715 from B. F. Goodrich)
solution in methyl ethyl ketone.
Solvents
136.6 gms methyl ethyl ketone and
210.0 gms methyl isobutyl ketone.
The pigment to binder ratio was 6:1 with a solvent to binder ratio
of 7:1 for a total solids content of about 50 percent, of which the
pigments were in the ratio of 25 percent CdSSe and 75 percent ZnO
by weight.
Because of the limited wetability of the pigments by the
polyurethane binder solution the following was done to produce a
smooth dispersion:
1. The 90 gms CdSSe, 136.6 gms methyl ethyl ketone, 210 gms methyl
isobutyl ketone and 5 gms polyurethane/methyl ethyl ketone solution
were milled for four minutes in a Kady mill. 2. The 270 gms of ZnO
and 5 more gms polyurethane/methyl ethyl ketone solution were added
to the above and Kady milled for 5 more minutes. 3. The remaining
(123.4 gms) polyurethane/methyl ethyl ketone solution was added to
the above and Kady milled for 5 more minutes. 4. The above mixture
was then charged into a ball mill, milled for 30 minutes and
filtered twice through cheesecloth.
The above procedure yielded a very smooth dispersion with a
viscosity of about 2,000 cps after wetting out over night. After
filtering again through cheesecloth the above dispersion was coated
onto a metallized Mylar belt using a laboratory knife coater. After
air drying for one-half hour, a top coat of Cargill-X-1513-30
polyurethane solution diluted to 11.5 percent solids was applied
using the same coating technique. The resulting coating was very
smooth to the touch and had an average thickness of 1.7 mils.
After air drying over night the belt was installed in a commercial
xerographic copying machine and successfully made 13,000 high
contrast copies.
EXAMPLE III
Another photoconductive belt was made using the same method as in
Example II with the following changes.
1. A CdSSe "Maroon" pigment from Ferro Corp. containing Se in a
mole ratio of 0.51 Se to Se+S was used instead of the Dark Red
pigment. 2. Pigments were in the ratio 35 percent CdSSe to 65
percent ZnO. 3. The viscosity of the dispersion was about 1500 cps
after 1.5 hours of ball milling.
Coating and top coating were accomplished in the same way as in
Example II, poly-N-vinyl in a final coating thickness of 2.0 mils.
The photoconductive belt was installed in a commercial xerographic
copier and run for 2,500 copies with no change in copy quality.
EXAMPLE IV
The procedure of Example I was followed except that the
photoconductive underlying material was poly-n-vinyl
carbazole/trinitrofluorenone complexed organic photoconductor. The
photoconductive properties of the image forming member were not
adversely affected while the reuse capacity of the photoconductor
was increased significantly.
EXAMPLE V
The procedure of Example I was followed except that the underlying
photoconductor material employed was amorphous selenium. Equivalent
results to those obtained in Example IV were experienced with the
amorphous selenium photoconductor.
EXAMPLE VI
A comparative test was run to demonstrate the satisfactory results
obtained with the polyurethanes of the instant invention. A
polyurethane which has a charge acceptance of less than 1,000
volts/mil, (and is available from the KJ Quinn Co. under the
designation "Quinn 2780") was subjected to the same procedures as
set forth in Example I. The results obtained are set forth in Table
F below.
TABLE F
__________________________________________________________________________
After Burnishing Before Burnishing. (2500 cycles)
__________________________________________________________________________
10% solids* 15% solids* 20% Solids* 15% solids* Charge acceptance
(Volts)1st charge 830 875 840 630 2nd charge 775 850 815 400 Dark
Decay (max) 35 45 80 110 (volts/sec) Speed (fcs) (avg.) .09 .09 .16
.10 Exposure to 60 V. .15 .17 .30 .28 (fcs) (avg.)
__________________________________________________________________________
*Polyurethane diluted to:
It will thus be seen from the above that a protective top coat both
protects and stabilizes xerographic photoconductors, and
particularly the mixture of cadmium sulfo-selenide and
photoconductive zinc oxide as a photoconductor. It will also be
seen that the top coating should have a charge acceptance of at
least 1,000 volts per mil of top coat thickness and preferably
1,500 volts per mil.
The invention may be variously otherwise embodied within the scope
of the appended claims.
* * * * *