U.S. patent number 3,773,507 [Application Number 05/159,455] was granted by the patent office on 1973-11-20 for electrophotographic reversal development process employing a pre-toner.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Osamu Fukushima, Satoru Honjo, Masamichi Sato.
United States Patent |
3,773,507 |
Sato , et al. |
November 20, 1973 |
ELECTROPHOTOGRAPHIC REVERSAL DEVELOPMENT PROCESS EMPLOYING A
PRE-TONER
Abstract
A reversal development process which comprises, after uniformly
charging a photoconductive insulating coating with a charge of one
polarity, applying a finely divided pre-toner having a white or
off-white appearance and a charge of the same polarity as that of
the uniform charge whereby the pre-toner deposits at the
charge-deficient areas in the coating, then subjecting the thus
treated coating to image exposure to form an electro-static latent
image, and finally developing the latent image by applying a finely
divided toner differently colored from the pre-toner, the toner
having a charge of the same polarity as that of the latent
image.
Inventors: |
Sato; Masamichi (Saitama,
JA), Fukushima; Osamu (Saitama, JA), Honjo;
Satoru (Saitama, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JA)
|
Family
ID: |
13154975 |
Appl.
No.: |
05/159,455 |
Filed: |
July 2, 1971 |
Foreign Application Priority Data
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|
|
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Jul 13, 1970 [JA] |
|
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45/60875 |
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Current U.S.
Class: |
430/100;
430/105 |
Current CPC
Class: |
G03G
13/22 (20130101); G03G 9/08 (20130101) |
Current International
Class: |
G03G
13/00 (20060101); G03G 13/22 (20060101); G03G
9/08 (20060101); G03g 013/00 (); G03g 013/02 () |
Field of
Search: |
;96/1,1SD,1LY
;117/17.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Miller; John R.
Claims
What is claimed is:
1. A reversal development process which comprises; after uniformly
charging a photoconductive insulating coating with a charge of one
polarity, applying a finely divided, photoconductive, pre-toner
having the same color as that of said photoconductive insulating
coating and a charge of the same polarity as that of said uniform
charge whereby the pre-toner deposits at the charge-deficient areas
in the coating, then subjecting the thus treated coating to image
exposure to form an electrostatic latent image; and finally
developing said latent image by applying a finely divided toner
differently colored from said pre-toner, said toner having a charge
of the same polarity as that of said latent image.
2. A reversal development process as in claim 1 where said
photoconductive pre-toner has a white or off-white appearance.
Description
BRIEF DESCRIPTION OF THE INVENTION
This invention relates to a reversal development method in
electrophotography, and more particularly to one which can provide
electrophotographic prints with reduced background or black spots
which are referred to as pin hole spots.
An optically positive toner image results by uniformly charging an
electrofax sheet material in a subdued light, then exposing said
charged material to an optically negative image of light and shadow
to form an electrostatic latent image, and then by developing the
latent image by the application of toner having the same polarity
of charge as that of the latent image.
In the case where the photoconductive coating is made of a
homogeneous mixture comprising a finely divided powder
photoconductor and a resinous binder, the coating has microscopic
irregularities which will not be present in an organic
photoconductive layer or amorphous selenium layer having a uniform
structure in molecular order. Such irregularities cause local
electrical breakdown when the coating is subjected to corona
charging, and at such areas where the impinged corona ions undergo
breakdown discharge the charged density will be nearly zero or
greatly lower than the surroundings.
Such pin hole areas in the coating will be developed as black spots
in a white background in reversal development in which toner
predominantly deposits at lower charge density areas.
Such black spots detrimentally affect on the image quality since
they are conspicuous in the highlight regions of a resulting
electrophotographic print.
The invention provides a reversal development method which
overcomes the above-cited shortcomings, and is characterized by
that a photoconductive insulating coating is imparted an
electrostatic charge of one polarity, supplied with finely divided
powder of the same color as that of the photoconductive insulating
coating and of the same polarity whereby the powder particles
deposit at the charge deficient pin hole areas in the charged
coating, then subjected to image exposure to form an electrostatic
latent image, and finally developed with colored finely divided
marking powder also having the same polarity of charge as that of
the latent image. The white or off-white powder will be referred to
as pre-toner while the marking powder as toner.
The essential feature of the present invention resides in that
pre-toner is allowed to deposit or mask the charge-deficient spots
formed during charging of the coating in order that such spots will
no longer attract toner in the subsequent image development. It
should be emphasized that in the present inventions the pre-toner
is applied onto the coating prior to the image exposure.
Application of pre-toner after image exposure is far less effective
for the present purpose. The reason is as follows; prior to image
exposure deposition of pre-toner will proceed only at the charge
deficient spots while, on the other hand, application of pre-toner
after image exposure will result in deposition of the pre-toner not
only at the charge-deficient spots but also at areas where charge
density changes abruptly. This will make it impossible to produce a
toner image of desirable quality since the toner will deposit with
a reduced deposition density at those areas.
Suitable particles for pre-toner in the present invention include
colorless or pale colored, finely divided natural or synthetic
polymers, white or off-white pigments, mixtures of polymer and
pigment particles, or similar pigments encapsulated with polymeric
materials, etc. Suitable polymers are ethyl cellulose,
nitrocellulose, triacetylcellulose, diacetylcellulose,
polyvinylacetate, polyvinylalcohol, gelatin polymethylmethacrylate,
polyvinylchloride, polycarbonate, etc., while examples of pigments
are barium sulfate, calcium carbonate, kaolin, aluminum hydroxide,
zinc oxide, titanium dioxide, zinc sulfide, lead white, etc.
As for the compositions of toner, those well known for those
skilled in the art by already disclosed literatures or patent may
be applicable for the present invention, including those for dry
development comprising carbon black and resinous material or those
for liquid development comprising pigment particles associated with
resinous materials absorbed on the surface of the particles.
Though the present invention is effective when combined with or
applied on a photoconductive coating comprising a finely divided
photoconductor and resinous binder, it is also applicable to a
homogeneous layer comprising organic photoconductor or amorphous
selenium.
EXAMPLE I.
A photoconductive insulating coating was provided by vacuum
depositing amorphous selenium on an aluminum plate. This coating
exhibited pin-hole like charge-deficient spots in repeated use.
Such spots became noticeable when the coating was charged to a high
potential.
The plate was charged by corona to +1000 volts, and then immersed
in a dispersion comprising kerosene as dispersant in which a small
quantity of linseed oil was dissolved as a dispersing-agent and
finely divided ethylcellulose of 1 to 10 micron diameter which had
a positive polarity of charge. After about a 10 second immersion,
the plate was pulled out and then subjected to an image exposure
utilizing a negative transparency.
The exposed plate was then developed with a liquid developer which
had been prepared by dispering a blended mixture of carbon black
and ethyl cellulose in kerosene in which was dissolved a small
quantity of linseed oil. The particle diameter of the pigmented
resin toner fell in the range between 1 and 10 microns.
Since the toner had a positive charge, reversal development
resulted.
The plate was drawn from the developer and superimposed ith a sheet
of ordinary paper while the surface of the plate was still wet. The
assemble was subjected to negative corona from the back surface of
the paper. Then the sheet was separated on which there was obtained
a positive print free of pin hole spots.
EXAMPLE II.
A white photoconductive insulating coating was prepared on paper
support by coating a blended mixture of photoconductive zinc oxide
and insulating binder. The coating was negatively charged to about
500 volts by corona. Prior to image exposure a mixture comprising
0.5 to 1 mm diameter glass beads overcoated with a thin film of
ethyl cellulose and pre-toner of 5 to 20 micron diameter
vinylchloride and vinyl acetate copolymer which were adhered
electrostatically to the surface of the beads was cascaded onto the
surface of the coating.
Then the coating was subjected to image exposure utilizing a
negative transparency. Developement was carried out by cascading
developer mixture comprising the glass beads carrier described
above and a pigmented resin comprising polystyrene and carbon black
having a diameter of about 10 to 30 microns.
The resulting image was free of pin-hole spots in the background
area.
On the contrary, a developed image obtained in the same procedures
except the pre-toner application was accompanied with a great
number of pin-hole spots.
EXAMPLE III.
Another sheet of the electrophotographic paper in Example II was
charged -- 400 volts in subdued light, and then immersed in the
following pre-toner dispersion of for 10 seconds:
Zinc oxide powder (particle diameter 0.05 to 0.5 microns) 10 parts
Linseed oil 10 parts Resin varnish 5 parts Kerosene 1000 parts
Cyclohexane 200 parts
The sheet was passed through a pair of insulating squeeze rollers
to remove the adhering liquid.
After exposing to an optically negative image, the sheet was
developed with the following developer:
Carbon black (particle diameter 0.01 to 0.1 micron 10 parts
Nitrocellulose 20 parts Resin varnish 20 parts Butyl acetate 20
parts
These ingredients were blended in a ball mill jar for 50 hours, and
10 mls of the resulting mixture was dispersed in a mixture
comprising 800 ml of kerosene and 200 ml of decalin under the
application of ultrasonic energy.
According to this example, pre-toner application can not only expel
pin-hole spots but also serve to prevent undesirable adhesion of
toner due to forces other than electrostatic.
As have been described above, the present invention may be
practiced by liquid or dry development. However, the present
invention is more advantageously carried out by the former method
of development which can provide electrophotographic prints of
quite high quality having tonal rendition wherein black pin-hole
spots in the highlight or background areas will fatally affect the
image quality. In the application of pre-toner on the
photoconductive coating, care must be taken not to greatly decrease
the surface charge density, or else one will fail to obtain a toner
image with sufficient contrast and density by the subsequent
development operation. When the pre-toner application is carried
out by liquid development, the electrical resistance of the
dispersion liquid should be high enough and the liquid should have
a poor affinity for the resinous binder or resinous ingredient in
the photoconductive coating.
Preferable solvents may be isoparaffinic, which have poor
dissolving power for many resinous materials, but more active
solvents such as straight chain hydrocarbons, alicyclic
hydrocarbons, decalin, or tetralin, and further, aromatic
hydrocarbons, or mixtures of aliphatic and aromatic hydrocarbons
may also be used if the resinous ingredient is cured.
In the case where dry development such as magnetic brush or cascade
development is employed whereby the carrier particles contact with
the surface of the photoconductive coating, the carrier particles
should not be electrically conductive.
On the other hand, powder cloud development involves no problem of
charge leakage due to pre-toner application.
Carrier particles for brush or cascade development which are
suitable for use in the application of pre-toner include glass
beads, natural silica sands, diamond beads, ferromagnetic iron
powder, and ferromagnetic alloy powder, all of which are surface
coated with insulating resinous materials.
When the present method is applied to multi-colored image formation
by over-printing technique wherein charging, image exposure, and
development are carried out more than twice on a single
photoconductive material, pre-toner should perform similarly as the
underlying photoconductive coating.
A suitable example of a pre-toner is dye-sensitized zinc oxide
encapsulated by insulating resin. Generally speaking, an
electrically insulating pre-toner is desirable for the following
reason: The charge on the pretoner will be neutralized after
deposition, draining to the ground through the insulating coating,
in which case colored toner will again deposit on the pre-toner in
the subsequent development and no improvement of image quality
results. Fortunately, however, this is not so serious a problem
since the pin-hole areas where electrical breakdown has occurred
become insulating again immediately after charging.
Regarding the application of pretoner and toner, one may employ dry
and/or liquid methods.
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