U.S. patent number 3,653,885 [Application Number 05/029,932] was granted by the patent office on 1972-04-04 for process of stabilizing a migration image comprising selenium particles.
This patent grant is currently assigned to Xerox Corporation. Invention is credited to Peter P. Augostini, Mortimer Levy.
United States Patent |
3,653,885 |
Levy , et al. |
April 4, 1972 |
PROCESS OF STABILIZING A MIGRATION IMAGE COMPRISING SELENIUM
PARTICLES
Abstract
An image comprising migration material residing on a metallic
conductive substrate and formed in accordance with the migration
imaging process is stabilized and fixed onto the substrate by
heating the substrate and the migration material to produce a
chemical reaction therebetween resulting in a permanent stable
image having high density and resolution.
Inventors: |
Levy; Mortimer (Rochester,
NY), Augostini; Peter P. (Webster, NY) |
Assignee: |
Xerox Corporation (Rochester,
NY)
|
Family
ID: |
26705483 |
Appl.
No.: |
05/029,932 |
Filed: |
April 20, 1970 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
590959 |
Oct 31, 1966 |
|
|
|
|
Current U.S.
Class: |
430/41;
430/97 |
Current CPC
Class: |
G03G
13/22 (20130101); G03G 17/10 (20130101) |
Current International
Class: |
G03G
13/22 (20060101); G03G 13/00 (20060101); G03G
17/00 (20060101); G03G 17/10 (20060101); G03g
013/22 () |
Field of
Search: |
;96/1,1.3,1.4,1.5
;117/17.5,37R,1.7,62 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Van Horn; Charles E.
Parent Case Text
This application is a continuation-in-part of our copending
application, Ser. No. 590,959 filed Oct. 31, 1966 and now
abandoned.
Claims
What I claim is:
1. A method for stabilizing a migration image comprising
a. providing a migration imaging member having a conductive
substrate comprising a metallic layer and an electrically
insulating solvent soluble overlayer containing migration material,
said migration material comprising selenium particles
b. forming an electrostatic latent image on said member;
c. developing said image by applying a solvent for said
electrically insulating layer to said member wherein a portion of
the selenium particles deposit in image configuration on said
conductive substrate and wherein another portion of selenium
particles and said electrically insulating layer are removed from
said substrate; and
d. heating said substrate and said selenium particles residing
thereon to a temperature not exceeding the temperature which will
warp or buckle said substrate whereby a chemical reaction occurs
between said metallic layer and said selenium particles.
2. The method as defined in claim 1 wherein said electrostatic
latent image is formed by uniformly charging said migration imaging
member and selectively illuminating said charged member with a
pattern of activating radiation.
3. The method of claim 1 wherein the conductive substrate comprises
copper.
4. The method of claim 1 wherein the conductive substrate comprises
brass.
5. The method of claim 1 wherein the conductive substrate comprises
cadmium.
6. The method of claim 1 wherein the conductive substrate comprises
silver.
7. The method of claim 1 wherein the conductive substrate comprises
gold.
8. The method of claim 1 wherein the migration material comprises
vitreous selenium.
9. The method of claim 1 wherein the migration material comprises a
vitreous alloy containing at least 50 percent selenium by
weight.
10. The method of claim 8 wherein the developed image of claim 1 is
treated with a crystallizing agent prior to step (d).
11. The method of claim 10 wherein the crystallizing agent
comprises vapors of mercury.
12. The method of claim 1 wherein the conductive substrate
comprises chromium.
Description
BACKGROUND OF THE INVENTION
This invention relates in general to imaging, and more
specifically, to an improved migration imaging system.
There has been recently developed a migration imaging system
capable of producing high quality images of high density,
continuous tone and high resolution. This system is described and
claimed in copending applications, Ser. Nos. 837,591 and 837,780
both filed June 30, 1969. In a typical embodiment of this imaging
system, a migration imaging structure consisting of a conducting
substrate with a layer of softenable or soluble material containing
migration material is coated onto the conductive substrate. An
electrostatic latent image is formed on the surface of the layer.
The softenable layer is then developed by dipping the plate into a
solvent which attacks only the soluble layer. A portion of the
migration material migrates through the softenable layer as it is
softened or dissolved, leaving an image on the conductive
substrate. Through the use of various materials, either
positive-to-positive or positive-to-negative images may be made
depending on the materials used and the charging polarities. Those
particles in the softenable layer which do not migrate to the
conductive substrate are washed away by the solvent with the
softenable layer.
Three basic migration imaging structures exist: A layered
configuration, which comprises a conductive substrate, a layer of
softenable material and an overcoating of migration material
(usually particulate) embedded in the upper surface of the
softenable layer; a binder structure, in which the migration
material is dispersed throughout the soluble layer which overcoats
a conducting substrate; and finally an overcoated structure, in
which a conductive substrate is overcoated with a layer of
softenable material followed by an overcoating of migration
material and a second overcoating of softenable material which
sandwiches the migration material. The migration imaging process
consists of the combination of steps which include charging,
exposing and development with a solvent liquid or vapor or a
combination of vapor followed by liquid. If vapor development is
used alone, the softenable layer may be stripped away leaving the
migration image on the substrate. The characteristics of these
images are dependent on such process steps as charging potential,
light exposure and development as well as the particular
combination of process steps. High density, continuous tone and
high resolution are some of the photographic characteristics
possible. The image is characterized as a fixed or unfixed powder
image which can be used in a number of applications such as
microfilm, hard copy, optical masks and stripout applications using
adhesive materials. Alternative embodiments of these concepts are
further described in the above cited copending applications.
Another recently developed imaging system, utilizes
non-photoconductive particles contained in a non-photoconductive
soluble layer on a conductive substrate. In this system, an
electrostatic latent image is formed such as by corona charging
through a mask or stencil. When the imaged sheet is exposed to a
solvent for the softenable layer only, the particles migrate to the
substrate in image configuration. The unwanted particles are washed
away with the soluble layer. This system is also described and
claimed in copending applications referred to above.
To prevent abrasion of the image formed by the migration imaging
method or loss of density, it is necessary to fix the image during
development or by additional steps after development. In fixing
during development, the developing liquid softens the conducting
substrate or a thin film on the substrate so that the image
particles can become embedded in the substrate or thin film. In
fixing after development, the developing liquid evaporates leaving
a coating of dissolved plastic over the image. Thus, by using
additional process steps after development, the image can be fixed
by either overcoating the image particles or by embedding them in
the conducting substrate or in a thin film on the substrate. As
techniques require additions to the solvent developer or a special
coating step, it can be seen that there is a definite need for a
simple and efficient image stabilizing step for migration images
which avoids softening or overcoating the substrate, and yet
produces images having high resolution and excellent density.
It is, therefore, an object of this invention to provide a method
of stabilizing migration images which overcome the above noted
disadvantages.
It is another object of this invention to provide a simple and
effective method of stabilizing migration images.
It is yet another object of this invention to provide a method of
stabilizing selenium containing images.
It is a further object of this invention to provide an improved
migration imaging process.
The foregoing objects and others are accomplished in accordance
with this invention by forming a migration image on a substrate
followed by heating or chemically reacting the image forming
material with the conductive substrate so as to produce a reaction
between the substrate and imaging material, resulting in a
permanent, stable image having high density and resolution. The
advantages of this improved method will become apparent upon
consideration of the following disclosure of the invention;
especially when taken in conjunction with the accompanying drawings
wherein:
FIG. 1A is a schematic sectional view of a layered structure for
carrying out the invention.
FIG. 1B is a schematic sectional view of binder structure used in
carrying out the invention.
FIG. 1C is a schematic sectional view of an overcoated structure
for carrying out the invention.
FIG. 2A is a schematic sectional view of the structure of FIG. 1A
during the charging step.
FIG. 2B is a schematic sectional view of the structure of FIG. 1A
during the exposure step.
FIG. 2C is a schematic sectional view of the structure of FIG. 1A
during the development step.
FIG. 2D is a schematic sectional view of the structure of FIG. 1A
following development.
FIG. 2E is a schematic sectional view of the structure of FIG. 1A
during the stabilizing step.
FIG. 1A shows a migration imaging plate comprising a conductive
substrate 11 having thereon a softenable layer 12 overlaying the
conductive substrate, and a layer 13 comprising migration material
usually in particulate form.
The substrate 11 upon which the softenable plastic and particulate
migration material are formed may be any suitable conductive
substrate which will react chemically with the migration material.
Typical substrates are copper, chromium, brass, cadmium, silver and
gold. The substrate may be in any form such as a metallic sheet,
web, foil, cylinder or the like. If desired, the conductive metal
may be coated over an insulator such as paper, glass or
plastic.
The softenable plastic layer 12 may be any suitable material which
is softened in a liquid or vapor solvent; and in addition, is
substantially electrically inert during the imaging and developing
cycle. Typical materials are Staybelite Ester 10, a partially
hydrogenated rosin ester, Foral Ester, a hydrogenated rosin
triester and Neolyne 23, an alkyd resin, all from Hercules Powder
Co.; SR 82, SR 84, silicone resins, both obtained from General
Electric Corporation; Sucrose Benzoate, Eastman Chemical; Velsicol
X-37, Hydrogenated Velsicol X-37, Velsicol Chemical Corp.,
Hydrogenated Piccopale 100, a highly branched polyolefin, Piccotex
100, polystyrene-vinyl toluene, Piccolastic A-75, 100 and 125, all
polystyrenes, Piccodine 2215, a polystyrene-olefin copolymer, all
from Pennsylvania Industrial Chemical Co.; Araldite 6060 and 6071,
epoxy resins of Ciba; R5061A, a phenyl-methyl silicone resin from
Dow Corning; Epon 1001, a bisphenol A-epichlorohydrin epoxy resin,
from Shell Chemical Corp., and PS-2, PS-3, both polystyrenes and
ET-693, a phenol-formaldehyde resin, from Dow Chemical. Other
materials useful as the softenable layer are described in copending
application, Ser. No. 837,780 filed June 30, l969, which is
incorporated herein by reference.
The above group of materials is not intended to be limiting, but
merely illustrative of materials suitable for the softenable
plastic layer. The softenable plastic layer may be of any suitable
thickness. In general, the thicker the layer the greater the
potential needed for charging. A thickness from about 1 to 4
microns has been found satisfactory, but layers outside this range
will also work.
The material 13, which constitutes the migration material, may be
any suitable migratable material which reacts with the metal
selected for the substrate. Typical migration materials are
photoconductors such as particulate vitreous selenium, and alloys
of selenium such as tellurium and selenium, cadmium sulfide,
cadmium sulfoselenide and arsenic triselenide. Other migration
material, photoconductive or non-photoconductive, is described in
the above mentioned copending application, Ser. No. 837,780. Of
course, the migration material is selected on the basis of its
reactivity with the metal employed at the substrate. The size of
the migration particles range from about 0.01 to 1.5 microns in
diameter and may be prepared by vacuum evaporation techniques such
as those disclosed in copending application, Ser. No. 423,167,
filed on Jan. 4, 1965, and now abandoned. Another convenient method
of forming the particulate migration layer is by simply dusting or
cascading the material on glass carrier beads over the soluble
layer softened by solvent vapor. This method is disclosed in
copending application, Ser. No. 483,675, filed on Aug. 30, 1965.
The thickness of the migration layer is from about 0.2 to 14
microns with the thicker layers being in the binder form.
In FIG. 1B, the binder form of the structure is shown in which the
migration particles 13 are dispersed throughout soluble layer
12.
The structure of FIG. 1C shows the overcoated structure in which
the migration particles 13 are sandwiched between two layers of
soluble matrix material 12 which overlays conductive substrate 11.
Both the binder and overcoated structure shown in FIGS. 1B and 1C,
respectively contain essentially the same basic materials as
illustrated for the layered structure shown in FIG. 1A.
In FIG. 2A the layered structure of FIG. 1A is uniformly charged
over its entire surface by a corona discharge device 14, such as
that shown in U.S. Pat. No. 2,777,957 to Walkup. The potential
required for migration imaging has been shown to depend on a number
of factors. For example, the form of the imaging structure such as
the three illustrated in FIGS. 1A, 1B and 1C, the thickness and
material used in the soluble layer, the type of migration material
used, the developing solvent, the combination of process steps, the
polarity of the potential and the light exposure, etc. If the
potential is too high, the migration particles are usually
deposited on the conducting substrate randomly without regard to
light exposure. If, on the other hand, the potential is too low,
none of the particles are deposited. In general, the potential may
range from a few volts to 400 volts with a soluble layer of about 2
microns in thickness depending upon the material used. Generally,
it may be said that the potential increases with the thickness of
the soluble matrix layer for a given matrix material. For a few
combinations of material, images can be obtained with potentials
for only one polarity. For some combinations of migration materials
and soluble layers, the maximum potential is higher for positive
than for negative polarity. For example, this was observed with
selenium vacuum evaporated on several different matrix
materials.
Other methods of forming an electrostatic image on the surface of
the photoconductive layer are also included within the scope of
this invention. Such methods include corona charging through a
stencil as shown in copending application, Ser. No. 483,675, filed
on Aug. 30, 1965. In addition, the migration imaging structure may
be charged through a liquid by an electrode using a low viscous
liquid such as a silicone oil.
In FIG. 2B the imaging or exposure step takes place with exposing
light 15 selectively impinging upon the charged surface containing,
for example, photoconductive particles 13. The exposure for
migration images depends upon the photoconductor, potential and its
polarity, the combination of the process steps in the form of the
imaging structure and the material of the soluble layer and solvent
used in development. As in xerographic imaging, any amount of light
suitable to activate photoconductor material 13, is usually
sufficient to form an image. For example, the minimum exposure for
maximum density with 4,000 angstrom light is approximately 1.5
.times. 10.sup.11 photons/cm..sup.2 with a structure consisting of
selenium vacuum evaporated on Staybelite, 2 microns thick. This
same exposure discharges a 50 micron conventional xerographic
selenium plate from 600 volts to 500 volts.
In FIG. 2C the development step for the migration imaging structure
is illustrated, wherein the structure is developed by immersing in
a solvent for soluble layer 12. The solvent liquid 16 may be
applied to the structure by spraying, pouring or dipping the
structure into the liquid. The development time is not particularly
critical inasmuch as the solvent is selected so as to dissolve only
the softenable or soluble layer and be relatively neutral with
regard to the photoconductive particles and conducting substrate.
The development time is divided essentially into two parts; the
time for imagewise migration of the particles to the conducting
substrate and the time for flushing away the unmigrated particles.
The development time ranges from less than 1 second with a layered
structure 3 microns thick, such as that illustrated in FIG. 1A, to
about 45 seconds using a binder structure such as that illustrated
in FIG. 1B having a binder structure about 12 microns thick. The
flushing time, and hence the developing time, can be reduced by
increasing the relative motion between the solvent and imaging
structure.
The solvent developer liquid 16 may comprise any suitable solvent
for the soluble layer 12. Typical solvents are Freon TMC (duPont);
trichloroethylene, chloroform, ethyl ether, xylene, dioxane,
benzene, toluene, cyclohexane, 1,1,1-trichloroethane, pentane,
n-heptane, Odorless Solvent 3440 (Sohio); Freon 113 (duPont),
m-xylene, carbon tetrachloride thiophene, diphenyl ether, p-cymene,
cis-2,2-dichloroethylene, nitromethane, ethanol, ethyl acetate,
methyl ethyl ketone, ethylene dichloride, methylene chloride,
1,1-dichloroethylene, trans 1,2-dichloroethylene and super
naptholite, (Buffalo Solvents and Chemicals). Other developer
liquids are described in copending application, Ser. No.
837,780.
After developing in the solvent liquid as shown in FIG. 2C, the
photoconductor 13 is formed in image configuration on substrate 11
as shown in FIG. 2D. At this point in order to stabilize image 13,
and at the same time increase the density of the image, a
stabilizing step which comprises reacting image 13 with substrate
11 is carried out as shown in FIG. 2E. The stabilizing step
involves heating the image bearing substrate 11 with any suitable
heating means such as a conducting coil 19 in order to react the
substrate 11 with the photoconductor material and cause a chemical
reaction between said photoconductive material and the substrate.
Other heating means such as hot air, gas burners, etc., may of
course, be used. During the heating step, the photoconductor
material in the image area agglomerates usually producing an
initial reduction in density due to fading, but after the reaction
with the substrate, the photoconductive material appears to wet and
spread over the substrate resulting in a stable image having high
density and illustrated by 13'.
As already mentioned above, the substrate may take any form or
configuration as long as the reactive metal is at the exposed
surface to receive the migration material after development.
For the purpose of illustrating the invention, a conventional
migration imaging member containing a copper substrate, and having
a 2-micron layer of Staybelite Ester 10, a 50 percent hydrogenated
glycerol rosin ester of the Hercules Powder Company, overlaying the
copper substrate, with a 0.2-micron layer of vapor deposited
selenium deposited in the upper surface of the Staybelite is
treated as follows:
The plate is first charged by a corona charging device to a
positive potential of about 100 volts (FIG. 2A). The plate is then
exposed to an optical image of about 10 foot-candle-seconds in the
illuminated areas using a tungsten lamp (FIG. 2B). Development of
the plate is carried out by immersion in Freon 113, a halogenated
hydrocarbon available from the E. I. duPont de Nemours Co., Inc.
for about 2 seconds and then removed and dried in air (FIGS. 2C and
2D). The particulate image is then stabilized by heating the
substrate to a temperature of about 100.degree. C. for about 1
minute to react the copper substrate with the selenium particulate
image. This reaction yields a black crystalline material having a
melting point of about 1,000.degree. C.
During the heating, the selenium in the image areas agglomerates
producing an initial reduction in density-fading, but after the
reaction, the selenium appears to wet and spread over the copper
substrate. The fading can be prevented by first converting the
surface of selenium in the image areas to a crystalline form,
followed by heating to produce the chemical reaction at the
copper-selenium surface. This crystallization can be produced by
exposure of the image to any known element or compound which will
crystallize the surface of the selenium or selenium alloy in the
image areas. These agents include vapor treatments with mercury,
iodine, chlorine, bromine, fluorine, amines such as hexylamine,
etc. For Example, exposure to mercury vapors for about 5 minutes is
usually sufficient to convert the surface to a crystalline
form.
The reaction temperature is that temperature at which the selenium
will react with the given substrate. This temperature is only
critical with respect to the substrate in that it should not exceed
a temperature which will warp or buckle the substrate.
Generally, temperatures in the range of about 90.degree. to
350.degree. C. are sufficient to react the selenium or selenium
containing alloy with the substrate.
EXAMPLE I
An imaging plate such as that illustrated in FIG. 1A is prepared by
roll-coating a 2 -micron layer of Staybelite Ester 10 (Hercules
Powder Company) on a 3 -mil Mylar polyester film (E. I. duPont de
Nemours & Co., Inc.) having a thin coating of copper about 0.1
micron thick. A thin layer of vitreous selenium approximately 1
micron in thickness, is then deposited onto the Staybelite by inert
gas deposition using the process set forth in copending patent
application, Ser. No. 423,167, filed on Jan. 4, 1965. The plate is
then electrostatically charged under dark room conditions to a
positive potential of about 60 volts by means of a corona discharge
device described by Carlson in U.S. Pat. No. 2,588,699. The charged
plate is then exposed to an optical image with an energy in the
illuminated areas of about 10 foot-candle-seconds by means of a
tungsten chamber and a weak blue filter. The plate is then
developed by immersing it in a bath of cyclohexane for about 2
seconds. The plate is removed from the developer bath and dried. An
excellent image corresponding to the projected image is observed on
the plate. This image comprises a thin layer of selenium particles
in image configuration on a copper substrate.
EXAMPLE II
The plate of Example I is then placed in a sealed glass chamber and
exposed to vapors of mercury for about 5 minutes. At the end of
this time, the plate is removed from the glass chamber and heated
by hot air to a temperature of about 100.degree. C. for several
minutes, at which time the selenium and the substrate react, with
the selenium appearing to wet and spread over the copper substrate.
The resultant image shows high density, excellent contrast and is
resistant to abrasion and thoroughly stable at relatively high
temperatures.
EXAMPLE III
An imaging plate using the copper coated Mylar substrate as in
Example I is roll-coated with a 2 -micron layer of Piccotex 100,
(Pennsylvania Industrial Chemical Company). This plate is coated
with a selenium layer and developed in cyclohexane as in Example I.
The plate is then exposed and developed as in Example II and shows
a stable image following mercury vapor treatment and heat
stabilization as set forth in Example II.
EXAMPLES IV - IX
The procedures set forth in Examples I and II are carried out with
a series of plates which are prepared, imaged, developed and
stabilized under varying conditions with the results and process
parameters set forth in the table below for all of the samples
prepared and tested in the examples. ##SPC1##
Although specific components and proportions have been stated in
the above description of the preferred embodiment of this
invention, other suitable materials and procedures such as those
listed above, may be used with similar results. In addition, other
materials may be added which synergize, enhance or otherwise modify
the images.
Other modifications and ramifications would appear to those skilled
in the art upon reading the disclosure. These are intended to be
included within the scope of this invention.
* * * * *