U.S. patent number 3,867,145 [Application Number 05/021,007] was granted by the patent office on 1975-02-18 for methanol and heat treated zinc oxide.
This patent grant is currently assigned to Rank Xerox, Ltd.. Invention is credited to Satoru Honjo, Hajime Miyazuka.
United States Patent |
3,867,145 |
Honjo , et al. |
February 18, 1975 |
Methanol and heat treated zinc oxide
Abstract
Photoconductive zinc oxide powder is wetted with a liquid
selected from the group consisting of water, methanol and mixtures
thereof and thereafter heat treated at a temperature between about
400.degree. and about 700.degree.C. The treated zinc oxide powder
may be mixed with a resinous binder and thereafter formed into an
electrophotographic layer.
Inventors: |
Honjo; Satoru (Asaka,
JA), Miyazuka; Hajime (Asaka, JA) |
Assignee: |
Rank Xerox, Ltd. (London,
EN)
|
Family
ID: |
12189315 |
Appl.
No.: |
05/021,007 |
Filed: |
March 19, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Apr 5, 1969 [JA] |
|
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44-26295 |
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Current U.S.
Class: |
430/87;
252/519.5; 423/622 |
Current CPC
Class: |
G03G
5/08 (20130101); C01G 9/02 (20130101) |
Current International
Class: |
C01G
9/02 (20060101); C01G 9/00 (20060101); G03G
5/08 (20060101); G03g 005/02 (); G03g 005/08 () |
Field of
Search: |
;96/1.8 ;252/501
;23/147,148 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin, Jr.; Roland E.
Claims
1. A process for treating photoconductive zinc oxide powder
comprising the steps of wetting zinc oxide powder with methanol and
thereafter heat treating said zinc oxide at a temperature between
about 400.degree.C and about 700.degree.C in an oxidative
atmosphere.
Description
BACKGROUND OF THE INVENTION
This invention relates to imaging systems, and more particularly,
to a method for forming improved photoconductive materials.
The formation and development of images on the surface of
photoconductive materials by electrostatic means is well known. One
conventional process involves placing a uniform electrostatic
charge on a photoconductive insulating layer comprising zinc oxide
powder and a resinous binder carried on a conductive paper
substrate, exposing the layer to a light-and-shadow image to
dissipate the charge on the areas of the layer exposed to the light
and developing the resulting electrostatic latent image by
depositing on the image a charged toner which is usually dispersed
in an insulating liquid. The charged toner may be suitably colored
and may have a polarity of charge identical or opposite to that of
the latent image to be developed.
Generally, photoconductive insulating layers comprising zinc oxide
powder and a resinous binder exhibit poor continuous tone
characteristics. This is unlike conventional silver halide emulsion
photographic layers in which various characteristics extending from
soft tones to hard tones, e.g. No. 1 to No. 5, are readily
available. In graphs in which the logarithm of exposure along the
abscissa is plotted against retentive potential or developed
density along the ordinate photoconductive layers containing zinc
oxide powder and an insulating film-forming binder are
characterized by curves having a short linear portion and a long
steep hard tone portion. Generally, this characteristic of the zinc
oxide binder layer cannot be modified to any great extent by
changing the ratio of the binder and the zinc oxide photoconductor
material or by altering blending conditions therefore.
Techniques have, however, been reported which regulate the
reproduction scale of electrophotographic photosensitive layers.
These techniques include the technique described in Japanese Patent
Application publication 11710/66 in which the photosensitive layer
is prepared by blending non-sensitized zinc oxide, dye-sensitized
zinc oxide and binder material; the technique disclosed in U.S.
Pat. No. 3,003,870 in which a dot pattern containing zinc oxide
photosensitive material of one photosensitivity is formed on a
continuous layer containing zinc oxide of a different
photosensitivity; and the technique disclosed in British Patent No.
967,690 in which a polarity of photosensitive layers dye-sensitized
to different degrees are superposed upon each other. These
techniques unfortunately are accompanied by serious drawbacks. For
example, in applying multiple layers of photosensitive materials or
in applying a single layer containing non-sensitized zinc oxide and
dye-sensitized components, redistribution of sensitizing dye from
dye-sensitized to non-sensitized zinc oxide frequently occurs and
markedly reduces any improvement in the ability of the resulting
photosensitive member to reproduce continuous tones.
SUMMARY OF THE INVENTION
It is therefore, an object of this invention to provide an
electrophotographic photosensitive material overcoming the
abovenoted deficiencies.
It is another object of this invention to provide an
electrophotographic photosensitive material having "soft"
characteristics suitable for the reproduction of continuous tone
images.
It is a further object of this invention to provide an
electrophotographic photosensitive material which forms continuous
tone reproductions with liquid developers.
It is still another object of this invention to provide an
electrophotographic photosensitive material superior to those of
known electrophotographic photosensitive material.
The above objects and others are accomplished by wetting zinc oxide
particles with water, methanol or mixtures thereof and thereafter
subjecting the zinc oxide particles to a heat treatment at a
temperature between about 400.degree. and 700.degree.C. The
resulting treated zinc oxide may then be mixed with a resinous
binder to form an electrophotographic photosensitive layer.
BRIEF DESCRIPTION OF THE DRAWING
The advantages of the improved electrographic photosensitive
material of this invention will become even further apparent upon
consideration of the following disclosure of the invention,
particularly when taken in conjunction with the accompanying
drawing wherein the variation of the gamma value characteristics of
electrographic photosensitive materials are illustrated with
respect to temperature of thermal treatment for the zinc oxide
particles employed therein.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In one embodiment, the principle zinc oxide treatment steps of this
invention include a uniform dispersion step, a drying step and a
heating step. In the uniform dispersion step, zinc oxide powder
produced by conventional techniques such as the gaseous oxidation
process is uniformly dispersed in water, methanol or a mixture
thereof. Zinc oxide powder is readily dispersible in water or
methanol, particularly in the latter, and forms a substantially
homogeneous dispersion.
In the drying step, the solid phase is separated from the
dispersion and the resulting paste is dried to remove the
dispersing liquid.
The dried zinc oxide particles are then heat treated at a
temperature between about 400.degree. and about 700.degree.C. Any
suitable heating device such as an electric furnace may be
employed. The heat treatment step is usually effected for at least
about 30 minutes in an oxidative atmosphere, preferably an
atmosphere of air or oxygen.
In another embodiment of this invention, the drying step and the
heating step described above are carried out simultaneously.
However, it is preferred to conduct the drying step prior to the
heating step, particularly when a mixture of water and methanol are
employed. The water content present on the surface of powdered zinc
oxide particles treated with a mixture of water and methanol and
thereafter subjected to a drying step usually changes in relation
to the ratio of water in the water-methanol mixture employed in the
uniform dispersion step. Since zinc oxide is easily wetted by and
dispersed in a mixture of water and methanol, water is more
uniformly distributed on the surface of zinc oxide particles after
the drying step.
The conditions of the drying step are not especially critical and
considerable latitude is permitted as to the drying temperature or
drying time employed. Generally, adequate removal of dispersing
liquids is achieved with drying temperatures less than about
150.degree.C.
Undesirable effects in the crystal lattice structure usually occurs
when a heating temperature exceeding about 700.degree.C is
employed. These undesirable effects are accompanied by a
deterioration of the characteristics of the photosensitive layer
formed from the treated zinc oxide particles. More specifically,
the photosensitivity of the photosensitive layer is adversely
effected. In addition, high heating temperatures will cause
sintering of the zinc oxide particles thereby forming agglomerates
which are undesirable in photoconductive layers containing zinc
oxide particles dispersed in a resinous binder. Thus, the
temperature of the heat treating step is preferably maintained at a
temperature less than about 700.degree.C.
Electrophotographic photosensitive members are formed with the zinc
oxide powder of this invention by uniformly dispersing the treated
zinc oxide particles in an insulating film-forming binder. The
resulting dispersion may be applied to an electrically conductive
surface. Any suitable resin binder conventionally employed as
binders for zinc oxide photoreceptors may be employed with the
treated zinc oxide dispersion technique may be employed to disperse
the zinc oxide particles in a resinous binder. If desired, the
spectral sensitivity of the treated zinc oxide particles of this
invention may be increased by treating the zinc oxide particles
with conventional sensitizing dyes. Electrophotographic
photosensitive layers formed with the treated zinc oxide particles
of this invention are characterized by excellent dark-decay
properties and low gamma values. Thus, curves formed by plotting
the logarithm of exposure along the abscissa against the retentive
potential or developed density along the ordinate will exhibit
decreased steepness for electrophotographic photosensitive layers
containing the treated zinc oxide particles of this invention. It
is unlikely that these two characteristics, low gamma value and
excellent dark-decay behavior, are simultaneously attained with the
prior art methods for producing photosensitive materials.
Although the gamma value of zinc oxide particles may be reduced
slightly by eliminating the uniform dispersion and drying steps
described above, the reduction is substantially less than that
achieved by utilizing all the steps in accordance with the process
of this invention.
The characteristics of the electrophotographic photosensitive
layer, particularly the gamma value thereof, appears to depend
greatly upon the water content in the solids after the drying step.
More specifically, the gamma value decreases with an increase in
water content. However, a marked deterioration of dark-decay
characteristics are observed when the water content in the zinc
oxide powder particles exceeds 20 percent by weight. It has been
found that the water content in the zinc oxide powder may be
adjusted by any suitable technique such as by regulating the
relative quantity of water in the water-methanol mixture described
above, the temperature employed in the drying step, the drying time
and the like.
Thus, preselected low gamma values for electrophotographic
photosensitive layers containing the treated zinc oxide particles
of this invention may be achieved by regulating the water content
of the zinc oxide particles prior to the heat treatment step. The
water content of zinc oxide particles may be regulated by other
wetting techniques. However, other wetting techniques such as
maintaining zinc oxide powder in an atmosphere of high temperature
and high humidity or flowing water vapor or humid gases through a
layer of zinc oxide powder require complex equipment and process
steps as well as special heating apparatus to obtain powder having
a uniformly distributed water content. Thus, accurate control of
the water content of treated zinc oxide particles is most
accurately and uniformly achieved with the uniform dispersion step
of this invention.
Surprisingly, a reduction of gamma values is not achieved at any
water content, with or without the drying step described above,
when the heat treating step of this invention is omitted. In other
words, marked reduction of gamma value characteristics is achieved
only when the uniform dispersion step, drying step and heating step
(the latter two steps being optionally combined) are employed to
treat zinc oxide particles.
The gamma value of the treated zinc oxide photoreceptors of this
invention also appear to be affected to some extent by the drying
step in which the paste of dispersing liquid and zinc oxide powder
is dried. Suitable selection of drying conditions in the drying
step will provide zinc oxide particles having a water content lower
than that in untreated zinc oxide particles. Electrophotographic
photosensitive layers prepared with treated zinc oxide particles
having a lower water content than that found in untreated zinc
oxide particles unexpectedly exhibit a lower gamma value than
electrophotographic photosensitive layers prepared with untreated
zinc oxide particles having a higher water content than the treated
zinc oxide particles. It is hypothesized that the reduced gamma
value may be due to the recrystallization of ions dissolved in the
dispersing liquid during the drying step whereby some zinc oxide
particles adhere to each other.
As described above, the treated zinc oxide particles of this
invention may be dye sensitized with many conventional dye
sensitizors. However, zinc oxide particles treated by the technique
of this invention may lose their affinity to some dyes such as
erythrosine. Thus, reduced sensitization may be observed with dyes
which are poorly absorbed by the treated zinc oxide particles.
The following examples further define and compare and describe
preferred embodiments and materials of the present invention. Parts
and percentages are by weight unless otherwise indicated.
EXAMPLE I
About 200 parts zinc oxide powder (Saze .times. 2000, Sakai Kagaku
Company) is dispersed in a mixture of about 640 parts of methanol
and about 200 parts water and subjected to ultrasonic wave energy
to obtain a homogeneous dispersion of zinc oxide. A paste
containing the zinc oxide powder and dispersing solvent is obtained
by centrifugal separation of the uniform dispersion. The paste is
dried in a drying chamber at about 50.degree.C for about 16 hours.
Upon completion of the drying step, the dried zinc oxide powder is
heated in a Mackel type electric furnace. The temperature in the
furnace is increased at a rate of about 4.degree.C per minute and
thereafter heated at a constant temperature for about 2 hours in a
quiescent atmosphere. The constant temperatures selected are
300.degree., 400.degree., 500.degree., 600.degree., and
700.degree.C. About 100 parts of the resulting treated zinc oxide
powder is mixed with about 60 parts of styrene-alkyd resin solution
(Styrenezol 4400, Japan Reichold), about 40 parts of polyisocyanate
solution (Desmodule L, Bayer) and about 130 parts of butyl
acetate-xylol (1:1) mixture. After blending in a homogenizer for
about 10 minutes, the mixture is applied as a coating onto aluminum
foil laminated to paper. Sufficient coating material is deposited
to form a dry and hard coating having a thickness of about 5 to
about 6 microns subsequent to heating for at least about 15 hours
at about 50.degree.C. The thus prepared electrophotographic
photosensitive member is cut into test samples and stored in the
dark for 2 days. Some of the test samples are tested for
light-decay characteristics by exposing the samples to tungsten
lamp light sources of different illuminance. The rate of potential
retention is calculated with the following formula: (V.sub.L
/V.sub.o /v.sub.D /V.sub.o.sub.') .times. 100% wherein V.sub.o,
V.sub.o.sub.', V.sub.L and V.sub.D respectively represent
potentials prior to exposure, prior to dark-decay measurements,
seven seconds after exposure for a fixed period to a light of
illuminance 1 and 7 seconds after the start of dark decay. The
characteristic curve is obtained by plotting the potential
retention rate along the ordinate and log 1/It along the abscissa.
A length of 100 in ordinate is equal to 20 in abscissa. Two
parallel straight lines having a distance therebetween of 0.1
measured by the log 1/It are drawn so as to position the
above-described curve therebetween. The slope of these lines are
taken as the gamma value.
The attached drawing illustrates the behavior of gamma value of an
electrophotographic photosensitive layer as the temperature of heat
treatment is changed. The behavior observed in electrophotographic
photosensitive layers containing zinc oxide particles treated
according to the process of this invention (curve A) is compared to
electrophotographic photosensitive layers containing zinc oxide
heated without the dispersion and drying steps of this invention
(curve B). As shown in the drawing, the reduction of gamma value
with an increase in temperature of heat treatment is more
pronounced with the zinc oxide powder treated by the process of
this invention and becomes particularly apparent when the
temperature of heat treatment is equal to or greater than about
500.degree.C.
EXAMPLE II
The procedure of Example I is repeated except that the ratio of
water and methanol is altered to obtain zinc oxide particles having
various water contents. The heating step is conducted at about
600.degree.C for about 2 hours. The water content in the zinc oxide
particles after the drying step as well as the accompanying change
of gamma value in an electrophotoconductive photosensitive layer
prepared with the treated zinc oxide particles is illustrated in
the following table. For purposes of comparison, the gamma value
obtained with zinc oxide powder not subjected to the uniform
dispersion and drying steps is listed in the following table. As
shown in the following table, the gamma value decreases with an
increase in water content thus indicating the advantages of this
invention over prior art processes in obtaining low gamma
values.
______________________________________ WATER CONTENT GAMMA
______________________________________ 0.18% (untreated) 2.5 0.16%
2.1 0.20% 2.0 1.50% 1.9 10.9% 1.4
______________________________________
As described above, the water content in the zinc oxide particles
after the drying step as well as the gamma value of photosensitive
layers obtained with the zinc oxide particles (heated at
600.degree.C for about 2 hours) are listed in the table shown
above.
EXAMPLE III
About 1000 parts zinc oxide particles are dispersed in about 4000
parts of water and processed as described in the foregoing
Examples. The zinc oxide particles are heated for 2 hours at
500.degree.C. About 700 parts of the resulting treated zinc oxide
powder is dispersed in about 50 parts of styrene-alkyd resin
solution (Styrezol 4400, Japan Reichold) in a porcelain ball mill
for about 10 hours. The ball milled dispersion is then mixed with
about 50 parts polyisocyanate hardener solution (Desmodule L,
Bayer) and sensitizing dye solution containing about 0.14 parts of
edible blue dye No. 1, about 0.28 parts of eosin and about 0.35
parts of fluorescein in a mixture of about 10 parts of water and
about 50 parts of ethanol. The resulting mixture is thoroughly
blended for about 20 minutes. The blended mixture is coated onto a
substrate and tested as described in Example I. The photoconductive
binder plate containing the treated zinc oxide particles exhibits
satisfactory soft characteristics with a gamma value of about
1.4.
Although specific materials and conditions are set forth in the
foregoing Examples, these are merely intended as illustrations of
the present invention. Various other suitable relative quantities
of water, methanol or mixtures thereof, drying conditions, heating
conditions, conventional zinc oxide photoreceptor resinous binders,
sensitizing dyes and the like including those listed above may be
substituted for those in the specific Examples with similar
results. Other materials may also be added to the zinc oxide powder
or zinc oxide binder plate to sensitize, synergize or otherwise
improve the imaging properties or other desirable properties of the
system.
Other modifications of the present invention will occur to those
skilled in the art upon a reading of the present disclosure. These
are intended to be included within the scope of this invention.
* * * * *