U.S. patent number 3,717,462 [Application Number 05/057,094] was granted by the patent office on 1973-02-20 for heat treatment of an electrophotographic photosensitive member.
This patent grant is currently assigned to Canon Kabushiki Kaisha. Invention is credited to Ichiro Endo, Kikuo Kinjo, Hirokazu Negishi, Teruo Yamanouchi.
United States Patent |
3,717,462 |
Negishi , et al. |
February 20, 1973 |
HEAT TREATMENT OF AN ELECTROPHOTOGRAPHIC PHOTOSENSITIVE MEMBER
Abstract
An electrophotographic photosensitive material comprising mainly
an organic photoconductive material of low molecular weight and a
high polymer resin which is subjected to heat treatment or
atmosphere treatment, and if desired, stimulus treatment to improve
the electrophotographic properties.
Inventors: |
Negishi; Hirokazu (Kanagawa-ku,
Yokohama-shi, Kanagawa-ken, JA), Endo; Ichiro;
(Nakano-ku, Tokyo, JA), Kinjo; Kikuo (Meguro-ku,
Tokyo, JA), Yamanouchi; Teruo (Fujisawa-shi,
Kanagawa-ken, JA) |
Assignee: |
Canon Kabushiki Kaisha (Tokyo,
JA)
|
Family
ID: |
13114799 |
Appl.
No.: |
05/057,094 |
Filed: |
July 22, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Jul 28, 1969 [JA] |
|
|
44/59491 |
|
Current U.S.
Class: |
430/74; 430/73;
430/76; 430/70 |
Current CPC
Class: |
G03G
5/06 (20130101) |
Current International
Class: |
G03G
5/06 (20060101); G03g 005/04 () |
Field of
Search: |
;96/1.5 ;252/501 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Cooper, III; John C.
Claims
What is claimed is:
1. An electrophotographic photosensitive member which comprises a
photosensitive film comprising an organic photoconductive material
of molecular weight ranging from 100 to 2,000 and selected from the
group consisting of diphenylene hydrazones,
2,5-bis-(4'-aminophenyl)-1,3,4-oxadiazoles, 2,5-bis-(4'-substituted
aminophenyl)-1,3,4-oxadiazoles wherein the substituent is a
monoalkyl, dialkyl or acyl group, 1,3,5triphenylpyrazolines,
p-dimethyl-aminostyrylketones,
N,N,N',N'-tetrabenzyl-p-phenylenediamine and triphenylamines and a
high polymer binder resin, said photosensitive film being heated at
a temperature not lower than the second order transition
temperature and lower than the melting point of the high polymer
binder resin for a period sufficiently long to convert said organic
photoconductive material to a uniform crystalline state.
2. An electrophotographic photosensitive member according to claim
1 in which the antioxidizing atmosphere is an inert gas.
3. An photosensitive photosenstive member which comprises a
photosensitive film comprising an organic photoconductive material
of molecular weight ranging from 100 to 2,000 and selected from the
group consisting of diphenylene hydrazones,
2,5-bis(4'-aminophenylene), -1,3,4-oxadiazoles wherein the
substituent is a monoalkyl, dialkyl or acyl group, 1,3,5
triphenylpyrazolines, p-dimethyl-aminostyrylketones,
N,N,N',N'-tetrabenzyl-p-phenylenediamine and triphenylamines and a
high polymer binder resin, said photosensitive film being heated at
a temperature not lower than the second order transition
temperature for a period sufficiently long to convert the film to
an amorphous state, said photosensitive film then being softened
with a solvent vapor capable of softening the photosensitive
film.
4. An electrophotographic photosensitive member which comprises a
photosensitive film comprising an organic photoconductive material
of molecular weight ranging from 100 to 2,000 selected from the
group consisting of diphenylene hydrazones,
2,5-bis-(4'-aminophenyl)-1,3,4-oxadiazoles, 2,5-bis-(4'-substituted
aminophenyl)-1,3,4-oxadiazoles wherein the substituent is a
monoalkyl, dialkyl or acyl group, 1,3,5-triphenylpyrazolines,
p-dimethyl-aminostyrylketones,
N,N,N',N'-tetrabenzyl-p-phenylenediamine and triphenylamines and a
high polymer binder resin, said photoconductive film being heated
at a temperature not lower than the melting point of the high
polymer binder resin, for a period sufficient to convert said
photoconductor to a uniform crystalline state the surface of said
film being stimulated by applying pressure thereto so as to yield
specific points on the surface resulting in a dot pattern
effect.
5. An electrophotographic photosensitive member which comprises a
photosensitive film comprising a diphenylene hydrazone and a high
polymer binder resin, said photosensitive film being heated at a
temperature not lower than the second order transition temperature
and lower than the melting point of the high polymer binder resin
for a period sufficient to convert said photoconductor to a uniform
crystalline state.
6. An electrophotographic photosensitive member according to claim
5 in which the diphenylene hydrazones are aliphatic aldehyde
diphenylene hydrazones.
7. An electrophotographic photosensitive member according to claim
5 in which the diphenylene hydrazones are aromatic aldehyde
diphenylene hydrazones.
8. An electrophotographic photosensitive member according to claim
5 in which the diphenylene hydrazones are heterocyclic aldehyde
diphenylene hydrazones.
9. An electrophotographic photosensitive member according to claim
7 in which the aromatic aldehyde diphenylene hydrazone is a member
selected from the group consisting of benzaldehyde diphenylene
hydrazone and p-dimethylaminobenzaldehyde diphenylene
hydrazone.
10. An electrophotographic photosensitive member according to claim
6 in which the aliphatic aldehyde diphenylene hydrazone is a
halogen substituted aliphatic aldehyde diphenylene hydrazone.
11. An electrophotographic photosensitive member according to claim
7 in which the aromatic aldehyde diphenylene hydrazone is a halogen
substituted aromatic aldehyde diphenylene hydrazone.
12. An electrophotographic photosensitive member according to claim
8 in which the heterocyclic aldehyde diphenylene hydrazone is a
halogen substituted heterocyclic aldehyde diphenylene
hydrazone.
13. An electrophotographic photosensitive member according to claim
11 in which the halogen substituted aromatic aldehyde diphenylene
hydrazone is a member selected from the group consisting of
benzaldehyde-3-halogen substituted diphenylene hydrazone,
p-dimethylaminobenzaldehyde-3-halogen substituted diphenylene
hydrazone, benzaldehyde-3,6-dihalogen substituted diphenylene
hydrazone, and p-dimethylamino-benzaldehyde-3,6-dihalogen
substituted diphenylene hydrazone.
14. An electrophotographic photosensitive member according to claim
13 in which the benzaldehyde-3-halogen substituted diphenylene
hydrazone is a member selected from the group consisting of
benzaldehyde-3-chlorodiphenylene hydrazone and
benzaldehyde-3-bromodiphenylene hydrazone.
15. An electrophotographic photosensitive member according to claim
13 in which the p-dimethylaminobenzaldehyde-3-halogen substituted
diphenylene hydrazone is a member selected from the group
consisting of p-dimethylaminobenzaldehyde-3-chlorodiphenylene
hydrazone and p-dimethylaminobenzaldehyde-3-bromodiphenylene
hydrazone.
16. An electrophotographic photosensitive member according to claim
13 in which the benzaldehyde-3,6-dihalogen substituted diphenylene
hydrazone is a member selected from the group consisting of
benzaldehyde-3,6-dichloro diphenylene hydrazone,
benzaldehyde-3,6-dibromodiphenylene hydrazone and
benzaldehyde-3-chloro-6-bromo-diphenylene hydrazone.
17. An electrophotographic photosensitive member according to claim
13 in which the p-dimethylaminobenzaldehyde-3,6-dihalogen
substituted diphenylene hydrazone is a member selected from the
group consisting of
p-dimethylaminobenzaldehyde-3,6-dichlorodiphenylene hydrazone,
p-dimethylaminobenzaldehyde-3,6-dibromodiphenylene hydrazone and
p-dimethylaminobenzaldehyde-3-chloro-6-bromo-diphenylene hydrazone.
Description
This invention relates to a novel organic photosensitive member
and, in particular, to a photosensitive member suitable for
electrophotography comprising a photosensitive film mainly composed
of an organic compund of low molecular weight and a high polymer
binder resin said photosensitive film being subjected to a
treatment for controlling the crystalline state of the film.
Heretofore, various organic photoconductive materials have been
known, for example, condensed polynuclear aromatic compunds such as
anthracene, phrene, and perylene, heterocyclic compunds such as
triphenyl-pyrazoline derivatives, acylhydrazone derivatives, and
high polymer compunds such as poly-N-vinylcarbazole. However,
photosensitivity of organic photoconductive materials is so low
that organic photoconductive materials are generally not suitable
for electrophotographic photosensitive materials. There have been
recently found organic compounds, the photosensitivity of which is
as high as that of inorganic substances such as zinc oxide and
selenium. As representative examples of such highly photosensitive
organic materials, there may be mentioned brominated
poly-N-vinylcarbazole in Japanese Pat. publication No. 25230/1967,
poly-3,6-duodo-9-vinylcarbazole in Japanese Pat. publication No.
7592/1968, poly-N-vinyl-3-aminocarbazole in Japanese Pat.
publication No. 9639/1967, and polyvinylanthracene in Japanese Pat.
publication No. 2629/1968. However, these organic photoconductive
materials are prepared through particular and complicated synthetic
processes so that these materials are not preferable from
economical and practical points of view.
Organic photoconductive materials are usually used as an
electrophotographic photosensitive material, and the material may
be used, as it is, without mixing with other components, or it may
be used by mixing it with a binder in a form of dispersion system
or solid solution state.
In such a photosensitive layer, with the lapse of time, coarse
crystals form spontaneously, and the coarse crystals continue to
grow depending on the outer conditions to form coarse crystals in a
wide distribution of particle size. Therefore, not only is the
transparency lowered, transparency being an important advantage of
organic photoconductive materials, but also the mechanical strength
of the photosensitive layer and the photosensitivity is
substantially deteriorated.
The present inventors have studied the crystallization phenomenon
which reduces the practicability of organic photoconductive
materials, and found that excellent photosensitive materials can be
obtained by controlling the crystallization state of organic
photoconductive materials of low molecular weight. This invention
solves various disadvantages of conventional organic
photoconductive materials such as low photosensitivity, poor
economy, and coarse crystals.
An object of this invention is to provide a photosensitive member
comprising an organic photoconductive material of low molecular
weight which has photosensitivity, stability and resolving power as
high as those of the conventional zinc oxide or selenium.
Another object of this invention is to provide a photosensitive
member having good photosensitivity, physical properties and a dot
pattern effect corresponding to the shape or resolving power
required for the photosensitive member.
A further object of this invention is to provide a photosensitive
member having excellent photosensitivity, resolving power,
stability, physical properties and a dot pattern effect which can
be easily produced by a simple method of manufacturing.
Still another object of this invention is to provide a
photosensitive member obtained by applying a treatment for
controlling the crystal state to a photosensitive film containing
an organic photoconductive material of low molecular weight and a
high polymer binder resin.
Further objects and advantages of this invention will be apparent
from the following description.
According to the treatment for controlling the crystalline state,
the crystalline state formed after subjection to the treatment for
controlling the crystalline state has a higher photoconductivity
than the original crystalline state.
The treatment for controlling the crystalline state and the
photoconductivity thus sensitized depend on crystalline states
before and after the treatment. This will be understood by the
following explanation. Heretofore, various efforts have been made
to prevent crystallization in an organic photosensitive film by,
for example, adding crystallization inhibitors such as a
plasticizer, polymerization inhibitor, and a softening agent since
spontaneous crystallization in an organic photosensitive film
deteriorates various useful properties thereof. However,
crystallization of the organic photoconductive material is due to
the inherent property of the material itself so that it is very
difficult to find a useful and practical means for preventing the
crystallization. Therefore, the deterioration of photoconductivity
and physical properties caused by crystallization has not yet been
removed. In general, crystallization does not uniformly occur over
the whole surface of the material, but initially occurs at a point
where crystallization easily occurs (hereinafter called "specific
point") and then the crystals thus formed grow and result in the
crystallization phenomenon which deteriorates photosensitive film.
Under natural conditions, crystallization proceeds starting from
the specific point previously formed when the film has been
produced. Such specific points are not uniformly distributed and
are distributed at low density so that coarse crystals form
locally. As a result, the film thus produced is in a state similar
to that containing impurities, i.e. the coarse crystals, are not
uniform distributed. In other words, a portion where the impurity
exists is different from the surroundings in points of
photoconductivity, and therefore, fog and irregular charging occur.
Further, the physical property at that portion of impurities is
different from the surroundings and therefore, the refractive index
is different and devitrification occurs and further the mechanical
strength is lowered.
According to this invention, the above-mentioned crystallization is
positively utilized, and a treatment for controlling the
crystalline state is applied so as to sensitize the
photoconductivity while keeping the mechanical strength unchanged
without causing deterioration of various properties of the
photosensitive film.
In a photosensitive film composed of an organic photoconductive
material of low molecular weight dispersed in a high polymer binder
resin in a form of solid solution, under material conditions the
organic photoconductive material of low molecular weight
crystallizes to form coarse crystals in the binder resin, but, by
applying a treatment for controlling crystalline the state,
microcrystals of the organic photoconductive material uniformly
form in the binder resin at a high density, and this state shows
high photoconductivity. The treatment for controlling the
crystalline state imparts external energy to the photosensitive
film and produces specific points on the whole film by the stimulus
without depending only upon the preliminarily present specific
points. Further, the treatment for controlling the crystalline
state enables molecules of the organic photoconductive material of
low molecular weight to move easily for the purpose of facilitating
the formation of microcrystals. More particularly, the treatment is
carried out by plasticizing the binder resin by applying heat or
solvent so as to facilitate the molecular arrangement for
crystallization of the organic photoconductive material of low
molecular weight. Even if the stimulus by external energy is
absent, the increased mobility of molecules often results in
controlling the crystalline state. The photosensitive film thus
subjected to the treatment for controlling the crystalline state
has clearly sensitized photoconductivity. In a sense, this system
is similar to a system wherein cadmium sulfide powders a known
excellent photoconductive material are dispersed in a binder resin,
but the cadmium sulfide powders are dispersed in an insulating
binder resin for the purpose of retaining the insulation property
at a dark place and therefore, the purpose is different from the
present invention.
The theoretical mechanism of the effect obtained by the treatment
for controlling crystalline state is not yet clear, but is
considered to be as follows. The conventional formation of coarse
crystals of organic photoconductive materials under natural
conditions results in nonuniform crystals, wide distribution of
particle size, and lowered physical property, photosensitivity and
resolving power, while the crystalline state obtained after
treatment for controlling crystalline state is uniform with a
narrow distribution of crystal size. Therefore, high
photosensitivity and high resolving power of the photosensitive
member according to this invention predominantly depend on the
uniformity of crystal state and narrow distribution of crystal
size.
The photosensitive member of this invention is generally obtained
by coating an organic photoconductive material of low molecular
weight together with a high polymer resin on a support base, if
desired, drying, hardening, and then applying a treatment for
controlling crystalline state. The treatment for controlling
crystalline state may be effected by various methods. The
representative methods are heat treatment and atmosphere treatment.
These two treatments may be applied singly or in combination for
controlling crystalline state.
A standard of treatment for controlling crystalline state may be
shown by a graph of temperature-crystal formation velocity and
temperature-crystal growing velocity illustrating the relation
between temperature and change of crystalline state.
The attached drawing illustrates a graph of temperature-crystal
formation velocity and temperature-crystal growing velocity.
In the graph, the ordinate is velocity and the abscissa is
temperature. With respect to the curves 1, 2, and 3, the ordinate
is crystal formation velocity, crystal growing velocity and melting
velocity, respectively. The symbol Tm denotes melting temperature.
This graph gives various indications referring to the control of
crystalline state. When the treatment for controlling crystalline
state is effected at a relatively low temperature for long time,
the crystal formation velocity exceeds the crystal growing velocity
so that microcrystals are formed. On the contrary, when the
treatment is effected at high temperature, relatively large
crystals are obtained. At an intermediate temperature,
particularly, a temperature between that at the peak of crystal
formation velocity and that at the peak of crystal growth velocity,
various crystalline states may be controlled depending on the
temperature. It should be noted here that the treatment temperature
should be kept below the melting temperature.
In addition, referring to heat treatment, it is necessary to adjust
appropriately heat treating conditions depending on kinds of
organic photoconductive materials of low molecular weight.
According to the experimental results, stability of an organic
photoconductive material of low molecular weight becomes high with
increase in symmetry, regularity and polarity of molecular
structure of the organic photoconductive material of low molecular
weight. Therefore, the optimal heat treating conditions may range
widely.
When the heat treatment is effected at a temperature near the
second order transition temperature Tg ) glass transition
temperature) of the binder resin, the crystallization is
effectively accelerated. In general, when heat treatment is carried
out at a temperature higher than the melting point of the
photosensitive film, the photosensitive film becomes amorphous. In
view of the foregoing the Tg and the melting point have a great
effect on treatment for controlling crystalline state. Therefore,
the heat treating conditions should be appropriately selected
depending upon the organic photoconductive material, binder resin,
plasticizer, amount thereof and the like.
Heat treatment is usually conducted by a direct heating means a
furnace, high frequency wave heating and infrared ray heating, but
secondary heating methods such as ion irradiation or electron ray
irradiation may be employed and further, if desired, cooling may be
employed.
Another treatment for controlling crystallization state is
atmosphere treatment. The crystalline state resulting from
atmosphere treatment is, to some extent, similar to the relation
between temperature and crystalline state in heat treatment, but
there are uncertain factors and it is not always possible to
determine clearly crystallization state common to that in heat
treatment.
As an example of atmosphere treatment, there is "solvent atmosphere
treatment". Control of the crystalline state by the solvent
atmosphere treatment is similar to that of heat treatment.
Referring to the drawing again, the abscissa is concentration of
solvent (the solvent being capable of softening the photosensitive
film) present above the coating surface as atmosphere, as shown in
the parentheses. The control of crystalline state by using
concentration of vapor is sufficiently effective. According to the
practical procedure, a solution containing an organic
photoconductive material of low molecular weight and a high polymer
binder resin is made into a coating film and then a solvent vapor
of a certain concentration is kept in contact with the coating film
for a certain period to control the crystalline state. In this
case, the crystalline state is considerably affected by the
thickness of coating layer. When the coating layer is thick, for
example, over 25 .mu., evaporation of the solvent present in the
coating layer is so slow that a relatively large amount of solvent
remains in the coating layer for a considerably long time, and
thereby, as shown in the attached graph, the crystal growing
velocity exceeds the crystal formation velocity and relatively
large crystals are formed from the initial stage of
crystallization. On the contrary, when the coating layer is thin, a
tendency opposite thereto appears.
The solvent atmosphere treatment lowers Tg of photosensitive film
and thereby facilitates crystallization.
The treatment in an antioxidizing atmosphere such as a reducing
atmosphere and an inert gas atmosphere prevents oxidation,
particularly, in case of high temperature treatment. As the
antioxidizing atmosphere, various gases such as nitrogen, hydrogen
and rare gas may be used.
These treatments for controlling crystalline state should be
applied taking into consideration the shape and inherent property
of the organic photoconductive material to be treated, and in
addition, resolving the power requested. It is particularly
important to control the crystal size so as to obtain high
photosensitivity and high resolving power. With respect to the
relation among crystal size, crystal orientation and resolving
power of the photosensitive film, the crystal size and crystal
orientation should be appropriately selected so as to obtain
resolving power required.
When the photosensitive member employs a paper as the support and a
resolving power of about 10 lines per mm. is desired, the crystal
size of about 20 particles per mm. (0.05 mm. in size) is suitable.
The control range of crystal size is 0.1 to 100 .mu. and a crystal
particle of above 1 .mu. can be observed by a microscope. Further,
referring to the thickness of the layer of the photosensitive film
and degree of crystallization, a thick layer results in easy
crystallization and formation of coarse crystals. If there exist
coarse crystals in the initial stage of film formation, it is
preferable to return the crystalline state once to an amorphous
state and then apply the treatment again producing microcrystalline
state.
According to another aspect of this invention, a stimulus treatment
such as external mechanical, physical and chemical stimulus
treatments may be employed in combination with the above mentioned
treatment for controlling crystalline state to obtain a
photosensitive member.
As the stimulus, there may be mentioned mechanical stimulus such as
contact, pressure contact, needle pressure, and friction, physical
stimulus such as various radiation irradiation, and ion or electron
ray irradiation, and chemical stimulus such as etching oxidation
and reduction.
The stimulus treatment not only facilitates the formation of
specific points, but also, on the contrary, suppresses the
crystallization. The effect of stimulus treatment is so wide as
mentioned above depending on the treatment conditions. The action
of stimulus treatment may be explained as follows. In general,
crystallization starts from the surface of the photosensitive film.
The stimulus by the stimulus treatment is given to the film surface
to yield specific points on a part of the surface the whole
surface. An example of such a specific point is that capable of
being a crystal nucleus from which crystallization starts, and only
the neighborhood of the specific points is subjected to the
treatment for controlling crystalline state and thus when the
treatment is applied locally, a photosensitive member having dot
pattern effect. This treatment for producing a dot pattern effect
may be conducted by one of the above-mentioned stimulus treatments,
that is, a pressure contact treatment. By appropriately selecting a
heat treatment or atmosphere treatment to be combined, control of
crystal size of amorphous or crystalline photosensitive film and
control of crystal orientation can be more effectively conducted to
produce a photosensitive member excellent in photosensitivity,
resolving power, and stability. The dot pattern effect may be
obtained by applying locally and partly heat treatment or
atmosphere treatment.
The heat treatment and atmosphere treatment, and in addition, the
stimulus treatment according to this invention can give a
photosensitivity of several to about 10 times that of a
photosensitive member not subjected to the treatment for
controlling crystalline state. Furthermore, resolving power and
stability of photosensitive members are increased by controlling
the crystal size and crystal orientation. Mechanical, physical or
chemical stimulus can give excellent dot pattern effect and improve
the properties.
These effects such as sensitization, resolving power, dot pattern
effect and improvement of properties can be easily obtained by
simply applying heat treatment, atmosphere treatment, and if
desired, additionally a stimulus treatment at a step in the
formation of the photosensitive film. Therefore, it is commercially
valuable. Furthermore, the electrophotographic photosensitive
member according to this invention has various desireable
properties requested to conventional organic photosensitive
materials, such as high reliability, high stability, simple
handling and high photosensitivity.
Compositions used for this invention are as shown below.
A As organic photoconductive materials of low molecular weight,
there may be mentioned the following compounds:
1. As compounds having heterocyclic ring, and aromatic ring, there
are, for example, 2,5-bis-(4'-aminophenyl-1')-1,3,4-oxadiazoles,
such as 2,5-bis-(4'-aminophenyl-1')-1,3,4-oxadiazole,
2,5-bis-(4'-monoalkylaminophenyl-1')-1,3,4-oxadiazole,
2,5-bis-(4'-dialkylaminophenyl-1')-1,3,4-oxadiazole and 2,5
bis-(4'-acylaminophenyl-1')-1,3,4-oxadiazole; diphenylene
hydrazones of aliphatic, aromatic or heterocyclic aldehydes or
ketones as disclosed in Japanese Pat. publication No. 4298/1964,
such as acetaldehyde-diphenylene hydrazone,
benzaldehyde-diphenylene hydrazone, o- or p-
chlorobenzaldehyde-diphenylene hydrazone, 2,4-dichloro
benzaldehyde-diphenylene hydrazone, p-dimethylaminocinnamic
aldehyde-diphenylene hydrazone, 2-pyridine aldehyde-diphenylene
hydrazone, p-dimethylamino benzaldehyde-diphenylene hydrazone,
benzaldehyde-3-chloro-diphenylene hydrazone,
benzaldehydro-3-bromo-diphenylene hydrazone,
p-dimethylaminobenzal-3-chloro-diphenylene hydrazone,
p-dimethylaminobenzal-3-bromo-diphenylene hydrazone,
benzaldehyde-3,6-dichloro -diphenylene hydrazone,
benzaldehyde-3,6-dibromo -diphenylene hydrazone,
benzaldehyde-3-chloro-6-bromo -diphenylene hydrazone,
p-aminodimethylbenzaldehyde -3,6-dichloro diphenylene hydrazone,
p-aminodimethyl benzaldehyde -3,6-dibromo diphenylene hydrazone and
p-aminodimethyl-benzaldehyde-3-chloro-6-bromo diphenylene
hydrazone; 1,3,5-triphenyl pyrazoline, 5-aminothiazole derivatives,
4,1,2-triazole derivatives, imidazolone derivatives, oxazole
derivatives, imidazole derivatives, pyrazoline derivatives,
imidazolidine derivatives, polyphenylene thiazole derivatives, and
1,6-methoxyphenazine derivatives.
2. As compounds having a condensed ring, there may be given, for
example, various derivatives of benzthiazole, benzimidazole,
benzoazole, aminoacridine and quinoxaline.
3. As compounds having double bond, there may be given, for
example, acylhydrazone derivatives and 1,1,6,6-tetraphenyl
hexatriene.
4. As compounds having amino or nitrile group, there may be given,
for example, aminated biphenyls, allylideneazines,
N,N,N',N'-tetrabenzl -p-phenylene diamine, triphenylamine and
p-dimethylaminostyryl ketone.
5. As condensation products, there may be given, for example,
condensation products of aldehyde and aromatic amine and reaction
products of aromatic amine and aromatic halide.
6. As condensed polymer, there may be given, for example,
intermediate condensation products of carboxylic acid halide and
triphenylamine.
B. As high polymer binder resins, there may be mentioned, for
example, polystyrene resin, polyvinyl chloride resin, phenolic
resin, polyvinylacetate resin, polyvinylacetal resin, epoxy resin,
xylene resin, alkyd resin, polycarbonate resin,
polymethylmethacrylate resin, and polyvinylbutyral resin.
C. As plasticizers, there may be mentioned, for example,
dioctylphthalate, tricresyl phosphate, diphenyl chloride,
methylnaphthalene, p-terphenyl and diphenyl.
D. As solvents, there may be mentioned, for example, benzene,
chlorobenzene, toluene, acetone, methanol, ethanol, ethyl acetate,
methylethyl ketone, trichloroethylene, carbon tetrachloride,
methylcellusolve, tetrahydrofuran, dioxane and
dimethylformaldehyde.
The organic photoconductive material of low molecular weight used
in this invention is that of molecular weight of about 100 to 2000,
preferred with 250 to 1000.
Preferable materials having high photosensitivity are
2,5-bis-(4'-aminophenyl)-1,3,4-oxadiazole, diphenylene-hydrazones,
1,3,5-triphenylpyrazoline, N,N,N',N'
-tetrabenzyl-p-phenylenediamine, p-dimethylaminophenyl styryl
ketone, and triphenylamine.
The amount of binder resin is not critical. It is preferably from
30 to 50 percent by weight based on amount of the organic
photoconductive material of low molecular weight. For the purpose
of improving further the property of film, a plasticizer may be
added in an amount of 5 to 80 percent by weight on the basis of the
amount of the organic photoconductive material of low molecular
weight.
As the coating method, there may be used conventional methods such
as, for example, rotary coating, wire-bar coating, flow coating,
and air-knife coating, and the thickness of coating may be adjusted
to several .mu. to several tens .mu. depending on the purpose.
As the support, there may be used a metal plate such as aluminum,
copper, zinc, and silver plates, a solvent proof paper, aluminum
laminate paper, synthetic resin film containing surfactant, and
glass, paper and synthetic resin film having a metal, metal oxide
or metal halide deposited on the surface by, for example, vapor
deposition. In general, any material may be used which has surface
resistivity less than that of the photoconductive layer, i.e. less
than 10.sup.8 .OMEGA., preferably less than 10.sup.5 .OMEGA., may
be used.
Conventional electrophotographic processes may be applied to the
electrophotographic photosensitive member to form
electrophotographic images. For example, the electrophotographic
photosensitive member according to this invention is passed several
times under a corona discharging device of + 6 KV. in a dark place
to accumulate positive charge to become 150-600 V. An appropriate
light source, for example, tungsten lamp, is used for projecting
light through a positive pattern to the photosensitive member and
the charge at the exposed portion is ventrallized. Then, a negative
toner is is applied by magnet brush method, cascade method, or
furbrush method to produce positive images. This images may be
fixed by heating or passing through an appropriate solvent vapor
atmosphere. Further, a liquid developer may be used. The polarity
of charge by corona discharging may be either positive or
negative.
The following examples are given for illustrating the present
invention, but should not be construed as a restriction of the
present invention.
EXAMPLE 1
2,5-Bis-[4'-n-propylaminophenyl-(1)]- 1,3,4-oxadiazole (m.p.
98.degree.C) 1.0 g. Maleic acid resin (Bechacite 1111, trade name,
supplied by Japan Reichhold Co.) (Second order transition
temperature 60.degree. - 65.degree.C) 1.0 g. Methylene chloride 20
ml. Methylene Blue 10 mg.
The above components were mixed to form a homogeneous solution,
applied uniformly to a one-sided art paper (80 .mu. in thickness)
to a thickness of 5 .mu., and dried naturally to form a
photosensitive coating, followed by heat treatment at 90.degree.C
for 30 minutes. The photosensitive coating thus heat treated was
given a positive charge of about 400 V. by a corona charging device
of +6KV, exposed to a high pressure mercury lamp, and soaked in a
commercially available negative liquid developer to produce a clear
visible image.
The exposure time of the photosensitive coating thus heat treated
and oriented was about 1/5 that in a case where the heat treatment
was not applied.
EXAMPLE 2
p-Dimethylaminobenzaldehyde diphenylene hydrazone* (m.p.
175.degree. - 7.degree.C) 1.0 g. Alkyd resin (Bechosol - 786, trade
name, supplied by Japan Reichhold Co.) 2 g. Cobalt naphthenate 0.02
g. Methylene chloride 20 ml.
The above components were mixed to form a homogeneous solution,
applied to a baryta paper (80 .mu. thick) undercoated on both sides
to a thickness of about 5 .mu., and heat treated at 140.degree.C
for 60 minutes in a room flushed with nitrogen gas. The resulting
photosensitive coating gave a clear visible image by following the
electrophotographic procedure in Example 1. The photosensitivity
was increased to about four times.
When benzaldehyde diphenylene hydrazone was used in place of
p-dimethylaminobenzaldehyde diphenylene hydrazone, a similar result
was obtained.
EXAMPLE 3
p-Diethylaminobenzylidene-nicotinic acid hydrazide (m.p.
153.degree. - 154.degree.C) 1.0 g. Xylene resin (Nikanol S-101,
trade name, available from Nippon Gas Chemical) 1 g. Methyl
cellosolve 30 ml.
The mixture of the above components was treated in a procedure
similar to Example 1, to form a photosensitive coating. The thus
obtained coating was subjected to heat treatment at 80.degree.C for
30 minutes. The thus produced coating was treated and developed in
a manner similar to Example 1 to produce a clear visible image. The
photosensitivity was increased to about four times by the heat
treatment.
EXAMPLE 4
1,3,5-Triphenylpyrazoline (m.p. 139.degree.C) 1.0 g.
Acrylnitrile-styrene copolymer (second order transition
temperature, 72.degree. - 75.degree.C) 1 g. Diphenyl chloride
(Kanechlor No. 400, trade name, commercially available from
Kanegafuchi Chemical) 0.5 g. Methylene chloride 20 ml.
The photosensitive preparation mixture of the above components was
applied uniformly to an aluminum foil (30 .mu. in thickness) to
form a coating of about 10 .mu. thick.
The coating thus obtained was in a complete amorphous solid
solution state. This coating was subjected to heat treatment at
70.degree.C for 30 minutes to produce a photosensitive member
having a coating containing microcrystallites.
The photosensitive member thus obtained was subjected to the
lightening of 200 lux of surface intensity of illumination by
tungsten lamp, with negative charge for 1.5 seconds to produce a
contrast of 200 V. compared with the untreated member which needed
an exposure of 10 seconds for the production of the same contrast.
The photosensitivity was increased to 6.5 times.
In this Example, the effect on the photosensitivity was observed by
a variation of the periods of the heat treatments. The heat
treatment at 70.degree.C for 10 minutes resulted in that the
photosensitive coating slightly clouded and the crystal growth was
observed, but the change of the sensitivity cannot be measured. The
heat treatment at 70.degree.C for 20 minutes resulted in that the
photosensitive coating clouded considerably, and the
photosensitivity was increased to about two times. The heat
treatment at 70.degree.C for 30 minutes resulted in that the
photosensitive coating changed throughout opaque, and the
photosensitivity was increased as above mentioned to 6.5 times that
of the untreated coating.
In addition, the heat treatment at 70.degree.C for 50 minutes
resulted in that the photosensitive coating did not change in its
appearance, but the photosensitivity was increased to about four
times that of the untreated coating. Such effect was somewhat
smaller than that of the former treatment.
EXAMPLE 5
The photosensitive member produced in Example 4 was placed in a
saturated vapor of methylene chloride for 60 minutes as an
atmosphere treatment to give a photosensitive member which was
microcrystallized. As the result of determination similar to
Example 4, the photosensitivity was increased to five times.
EXAMPLE 6
The photosensitive coating having the same components as Example 4
was subjected to heat treatment at 125.degree.C for 20 minutes to
produce a coating in solid solution state. This coating was
subjected to heat treatment at 70.degree.C for 30 minutes similarly
to Example 4 to gain an increase of about 4 times in the
photosensitivity. In comparison with Examples 4 and 5, the coating
thus obtained retains a considerable amount of residual charge upon
decay by light after charging. Therefore, the performance of this
coating as an electrophotographic photosensitive coating was less
advantageous. The growth of microcrystallites was investigated by a
microscope of 500 magnifications resulting in that there was
observed more amount of amorphous area on the surface of the
coating subjected to heat treatment at 125.degree.C for 20 minutes,
than that on the coating obtained in Example 4.
EXAMPLE 7
To the coating of the photosensitive member of Example 4 was
pressed a metal wire network of 150 mesh, and then heat treatment
was applied thereto at 70.degree.C for 15 minutes. The thus treated
coating was investigated by a microscope of 500 magnifications with
the result that the growth of crystallite was partially caused from
a part contacted with the metal wire network as a crystal nucleus.
To the thus obtained coating was applied a light at 200 lux for 2
seconds to form an image. There was obtained a clear visible image
having a dot pattern effect. This was advantageous in the
production of a half tone image.
EXAMPLE 8
The preparation mixture in Example 4 was applied to an aluminum
foil (30 microns in thickness) to form a coating of about 50
microns in thickness, which was then changed to containing coarse
crystals as a result of evaporation of the solvent used. Thus
obtained coating was excellent in photosensitivity, but poor in
image quality. The coating was then subjected to heat treatment in
a room saturated by nitrogen gas at 150.degree.C for 20 minutes
with the result that the coating changed into a solid solution
(amorphous) state, and the image quality was increased, but the
photosensitivity was reduced.
Furthermore, this coating was subjected to heat treatment at
70.degree.C for 30 minutes resulting in the growth of
microcrystallite and satisfactory image quality and
photosensitivity.
EXAMPLE 9
The photosensitive preparation mixture as used in Example 4 was
applied to an aluminum film of about 30 micron in thickness to form
a coating of about 70 micron in thickness. The thus obtained
coating was subjected to heat treatment at 70.degree.C for 30
minutes to produce a photosensitive coating containing
microcrystallite. To the surface of the photosensitive layer a
polyester film of about 25 micron in thickness was adhered
completely by using epoxy resin bonding agent to produce a
photosensitive member of three layered structure. The
photosensitive member thus obtained was subjected to charging of
positive charge by a corona discharger of +6 KV, uniformly on the
surface of the polyester film of the photosensitive member
contemporaneously with whole surface exposure by a tungsten lamp.
Then, to the surface of the polyester film, the original image was
projected by a tungsten lamp of about 1000 lux, contemporaneously
with the application of charging by negative corona discharger of
-6 KV. Then, tungsten lamp of 100 W was applied thereto for about 2
seconds to produce an electrostatic image corresponding to a
contrast pattern of the original image. This latent image was
developed by magnet brush method to produce an excellent visible
image.
EXAMPLE 10
Benzaldehyde-3,6-dichloro- diphenylene hydrazone* 1.0 gr. ##SPC1##
(m.p. 165.degree.C) 2,4,7-Trinitrofluorenone 5 mg. Diphenylamine
Blue 20 mg. ##SPC2## Cumarone-indene resin 1.5 gr. (second order
transition temperature; 60.degree.-65.degree.C) Methyl ethyl ketone
5 ml. (*This compound can be prepared by a process which comprises
treating 3,6-dichlorocarbazole, m.p., 201.degree.C, in glacial
acetic acid with sodium nitrite to provide 3,6-dichloro-9-nitroso
carbazole, m.p., 110.degree.C, reducing the resulting compound in
ether by zinc dust and hydrochloric acid, and immediately
condensing the product with benzaldehyde.)
The preparation mixture of the above components was applied to a
polyester film undercoated with a conductive polymer, and dried at
50.degree.C for 3 minutes to form a photosensitive coating. The
thus obtained coating was determined as amorphous by X-ray
diffraction spectrum of the collected sample from the coating. The
thus obtained film was kept in an oven at 80.degree.C for the
period indicated in the Table below, and then cooled. There is
shown the transmittivity and appropriate exposure of thus treated
films in the Table below. The appropriate exposure was based upon
exposure to tungsten lamp by a positive charge and electrophoresis
development.
Table
transmittivity appropriate Sample No. the period ratio exposure
(minutes) % lux.sec 1 5 80 150 2 10 73 125 3 30 50 300 untreated 0
85 1000
The transmittivity was measured by a white light, and calculated by
assuming the transmittivity of the used film base as 100
percent.
The photosensitivity was increased in Samples 1 and 2 but reduced
in Sample 3. The crystalline pattern was observed in the X-ray
diffraction spectrum of Sample 3. This result teaches that the
increase of a photosensitivity needs a proper degree of crystal
growth, or an increase of amount of microcrystallites.
In the replacement of benzaldehyde-3,6-dichloro diphenyl hydrazone
of this Example, by benzaldehyde-3-bromodiphenyl hydrazone (I),
benzaldehyde-3-chloro-diphenylene hydrazone (II),
p-dimethylaminobenzaldehyde-3,6-dichlorodiphenylene hydrazone
(III), dimethylamino-3,6-dibromo diphenylene hydrazone (IV) and
p-dimethylamino-3-chlorodiphenylene hydrazone (V), the procedures
of this Example were repeated to result in the appropriate exposure
indicated in the Table below for the compounds (I) - (V) by the
heat treatment for 10 minutes.
Table
Compound I II III IV V Appropriate exposure 190 230 115 125 170
lux. sec.
EXAMPLE 11
N,N,N',N'-Tetrabenzyl-p-phenylene diamine 1.0 gr. Polyvinyl butylal
resin (commercially available under the trade name S-lec BLS by
Sekisui Chemical) 1.0 gr. Crystal violet 10 mg. Chloroform 10
ml.
The above components were mixed homogeneously and the mixture was
applied uniformly to a one-sided art paper of 80 micron in
thickness to form a coating of about 5 micron, thick and dried
naturally to form a photosensitive coating. Thus obtained coating
was subjected to heat treatment at 95.degree.C for 20 minutes. The
thus treated photosensitive paper was charged to about 350 V of
positive charge by a corona discharger of 5 KV in charge voltage,
then exposed at 250 lux. sec. by tungsten lamp of 100 W, and
developed in a liquid developer to produce a visible image. For the
similar photosensitive paper which was not subjected to the above
heat treatment, the exposure of about 1,000 lux.sec. was necessary
to produce a clear visible image by the similar electrophotographic
duplication process.
EXAMPLE 12
p-Dimethylaminophenylstyryl ketone 1.0 gr. Polystyrene resin
(commercially available under the trade name "Piccolastic D-100" by
ESSO) 1 gr. Methylene blue 10 mg. Methyl ethyl ketone 10 ml.
The preparation solution of the above components was applied
uniformly to an aluminum foil plate to a thickness of about 5
micron, and dried by hot air blow at 50.degree.C for 5 minutes to
form a photosensitive coating. The thus obtained photosensitive
plate was subjected to heat treatment at 80.degree.C for 30
minutes. This plate was subjected to an electrophotographic
duplication process similar to Example 11. The exposure of about
200 lux.sec. was necessary to produce a clear visible image.
EXAMPLE 13
Triphenylamine 1.0 gr. Acrylonitrile styrene copolymer resin
(commercially available under the trade name "Estylene AS-61NT" by
Yahata Chemical) 1.0 gr. Malachite Green 10 mg. Benzene 20 ml.
The preparation solution of the above components was applied to a
polyethyleneterephthalate film (90 .mu. thick) to the surface of
which electroconductivity was imparted by coating the film surface
with a solution composed of 4 gr. of cuprous iodide and 150 ml. of
acetonitrile to which 30 ml. of a 5 percent solution of polyvinyl
formal was added, to form a photoconductive coating, then which was
dried naturally. The thus obtained photosensitive film was
subjected to heat treatment at 70.degree.C, for 30 minutes. To the
thus treated film, an electrophotographic duplication process was
applied. The exposure of about 250 lux.sec. was necessary to
produce a clear visible image. For the similar photosensitive film
which was not subjected to the above heat treatment, the exposure
of 1200 lux.sec. was necessary to produce a clear visible
image.
* * * * *