U.S. patent number 3,720,514 [Application Number 05/052,311] was granted by the patent office on 1973-03-13 for electrophotographic paper having an inorganic colloidal oxide coating.
This patent grant is currently assigned to Xerox Corporation. Invention is credited to Satoru Honjo, Yasuo Tamai.
United States Patent |
3,720,514 |
Honjo , et al. |
March 13, 1973 |
ELECTROPHOTOGRAPHIC PAPER HAVING AN INORGANIC COLLOIDAL OXIDE
COATING
Abstract
An electrophotographic paper is provided which comprises a
waterproof paper treated with an inorganic colloidal oxide
dispersion having an electroconductive layer coated over the
treated surface and a photoconductive layer residing on the surface
of the electroconductive layer.
Inventors: |
Honjo; Satoru (Asaka,
JA), Tamai; Yasuo (Asaka, JA) |
Assignee: |
Xerox Corporation (Stamford,
CT)
|
Family
ID: |
13033776 |
Appl.
No.: |
05/052,311 |
Filed: |
July 6, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Jul 17, 1969 [JA] |
|
|
44/56668 |
|
Current U.S.
Class: |
430/60; 430/62;
162/138; 430/63 |
Current CPC
Class: |
G03G
5/105 (20130101) |
Current International
Class: |
G03G
5/10 (20060101); G03g 005/00 () |
Field of
Search: |
;162/138,181,181C
;117/218 ;96/1.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"Hackh's Chemical Dictionary," 1969, page 614. .
Labarre, "A Dictionary of Paper and Paper-Making Terms," 1936, page
232. .
Rowland et al.; "The Alumina Content of Rosin-Free Hand-Sheets in
Relation to Tub Sizing," Paper Trade Journal; Vol. 119; No. 20;
Nov. 16, 1944; pp. 199-203.
|
Primary Examiner: Lesmes; George F.
Assistant Examiner: Miller; John R.
Claims
What is claimed is:
1. An electrophotographic paper comprising a paper base treated
with a waterproofing compound, overlying said treated base a
coating of inorganic colloidal oxide, overlying said oxide coating
an electroconductive hydrophillic resinous layer, and overlying
said electroconductive layer a photoconductive layer.
2. An electrophotographic paper as defined in claim 1 wherein said
inorganic colloidal oxide is selected from the group consisting of
silica and alumina.
3. An electrophotographic paper oxide as defined in claim 2 wherein
said oxide is present in an amount of more than about 70 percent by
weight of non-volatile ingredients.
4. The paper as defined in claim 1 wherein said electroconductive
layer has as its principal ingredient a member selected from the
group consisting of quaternary ammonium salt polymers, polyvinyl
benzene sulfonic acid, and the water soluble salt of polyvinyl
benzene sulfonic acid.
5. A method for providing an electrophotographic paper comprising
providing a waterproofed paper treated on at least one side,
coating said treated side with a inorganic colloidal oxide
dispersion, forming an electroconductive hydrophillic resinous
layer upon said oxide coating, and coating a photoconductive layer
over said electroconductive layer.
6. The method as defined in claim 5 wherein said electroconductive
layer is formed on said oxide coating at a concentration of from
about 1 g to 4 g per M.sup.2.
7. The method as defined in claim 5 wherein said colloidal oxide
dispersion is coated on said treated side at a concentration of
from about 0.1 g to 3 g per M.sup.2.
8. The method as defined in claim 5 wherein said colloidal oxide
dispersion is coated on said treated side at a concentration of
from about 0.2 g to 1.5 g per M.sup.2.
9. The method as defined in claim 5 wherein said colloidal oxide
dispersion is selected from the group consisting of silica and
alumina.
10. The method as defined in claim 9 wherein said colloidal oxide
dispersion is present in an amount of more than about 70 percent by
weight of non-volatile ingredients.
11. The method as defined in claim 5 wherein said electroconductive
layer has as a principal ingredient one member selected from the
group consisting of quaternary ammonium salt polymers, polyvinyl
benzene sulfonic acid and a water soluble salt of polyvinyl benzene
sulfonic acid.
12. A method for reproducing continuous tone images in
electrophotography comprising; providing an electrophotographic
paper, said paper comprising a waterproof base having coated
thereover a layer of inorganic colloidal oxide, an
electroconductive hydrophillic resinous layer overlying said layer
of oxide and a photoconductive layer overlying said
electroconductive layer; charging said paper; selectively
illuminating said paper; and developing said paper.
13. The method as defined in claim 12 wherein said colloidal oxide
is selected from the group consisting of silica and alumina.
14. The method as defined in claim 12 wherein said oxide is present
in an amount more than about 70 percent by weight of non-volatile
ingredients.
15. The method as defined in claim 12 wherein said
electroconductive layer has as its principal ingredient one member
selected from the group consisting of quaternary ammonium salt
polymers, polyvinyl benzene sulfonic acid and a water soluble salt
of polyvinyl benzene sulfonic acid.
16. The method as defined in claim 12 wherein a liquid developer is
employed.
Description
BACKGROUND OF THE INVENTION
This invention relates to electrophotography and more specifically
to electrophotographic members and methods for providing same.
In the well known art of electrophotography, commonly called
xerography, more fully described in U. S. Pat. No. 2,296,671, it is
known that a visible image may be formed by employing sensitized
and unsensitized paper. Where unsensitized paper is employed an
electrophotographic member, normally a photoconductive member, is
charged, exposed, and developed and then the image so formed is
transferred to the unsensitized paper and normally fused thereon
using appropriate means. When it is desired to form an image
directly on the paper eliminating the transfer step a sensitized
paper is employed which is charged and selectively illuminated and
then developed. Such electrophotographic sensitive paper or
electrostatic recording paper medium usually comprises a base paper
which is given a special treatment so as to acquire a high degree
of electroconductivity in a particularly wide range of humidity and
an insulative recording layer formed thereover by spreading or
other means. Treatments usually employed for conferring such
electroconductivity are broadly divided into two classes: to one
class belongs the methods by which such substances as hygroscopic
inorganic salts, hygroscopic polyhydroxy compounds, cationic active
agents, or quaternary ammonium salt polymers are caused to
impregnate the fiber structure of the paper through its entire
thickness; and the other class of treatment given for conferring
electroconductivity is such that a continuous film of low
resistance is formed on the surface of the side closer to the
recording layer. The former compound may be used either alone or in
combination. Film forming agents may be employed such as
polyacrylic acid, salts thereof or polyvinyl alcohol. However,
since these substances have relatively low electroconductivity in
an environment having low humidity, recent methods have come to
employ polymers derived from monomers containing the structure of
quaternary ammonium salts. Polymers of this type are able to form
films which exhibit a high degree of electroconductivity in a wide
range of humidity. It has been found, however, that where it is
desired to obtain an image of continuous tone equivalent in quality
to that of the conventional silver halide process by
electrophotography, methods of treatment of the base paper known in
the art often prove unsatisfactory in terms of performance.
Inadequacy of performance is due to a number of problem areas which
exhibit themselves in the unsatisfactory quality of reproduction
obtained.
When it is desired to obtain a continuous tone image by developing
an electrostatic latent image employing a liquid developing agent
comprising extremely fine toner particles, it is found that the
nature of the base employed affects the highlight areas of the
reproduction so obtained. If the base employed has insufficient
smoothness or the electroconductive film is not a complete
continuous film in the lateral direction, it is found that the
highlight area for example fails to be developed to a low density
uniformly. This is caused by the toner depositing in fine or finer
areas to a relatively higher density apparently in conformity to
the structure of the base giving rise to an extremely objectionable
appearance. It is found that if the smoothness and electrical
quality of the base are not adequate there may result a slight
variation in thickness and electrostatic capacity of the sensitive
layer which may cause corona discharge depriving the surface charge
density of uniformity and, consequently, making photosensitivity
non-uniform. This absence of uniformity becomes conspicuous when
substantially all surface charge is removed and only a small
portion of it is permitted to remain as a consequence of exposure
to light. This explanation is found to agree with experimentation
and satisfactorily explains why such unevenness is observed clearly
in about two stages of the highlight area having a very low density
and not observed either in the area of high density or in the
completely discharged or when, for example, an optical wedge is
developed on an electrophotographic sensitive paper. That roughness
of the highlight area of the print obtained will substantially
affect the clarity of the print is known. This shortcoming tends to
become detrimentally conspicuous particularly when obtaining a
multi-color image with continuous tone as compared with a
monocromatic image. In order to remedy this problem, i.e., to
obtain adequate smoothness of the paper base and the proper
electroconductive properties, a polished metal layer or a vacuum
deposited metal overlying a smooth plastic base or the like may be
employed. Thus, it is seen that a base having a high smoothness and
extremely high degree of electroconductivity is particularly
preferable for the reproduction of continuous tone images. However,
it is extremely difficult to fabricate such a base from paper
material which is porous and characteristically has fiber-like
rough surfaces and is inherently less electroconductive than
metals.
SUMMARY OF THE INVENTION
It is, therefore, an object of this invention to provide
electrophotographic recording media devoid of the above noted
disadvantages.
Another object of this invention is to provide electrophotographic
sensitive paper having the advantages of a smooth, metallic base in
the reproduction of continuous tone images.
Still another object of this invention is to provide an
electrostatic paper recording medium which is particularly suitable
for the reproduction of continuous tone multi-color images.
Yet, another object of this invention is to provide a method
whereby electrophotographic recording media comprising paper may be
rendered suitable for the reproduction of continuous tone
images.
Still another object of this invention is to provide a novel
electrophotographic system.
Yet, another object of this invention is to provide a novel method
for producing electrophotographic paper.
These and other objects are accomplished in accordance with the
system of the present invention by providing an electrophotographic
paper comprising treating a waterproofed paper with a processing
liquid comprising colloidal silica and/or colloidal alumina having
a non-volatile content of at least 70 percent by weight forming on
the treated surface of the base an electroconductive layer having
as a principal ingredient a member selected from the group
consisting of quaternary ammonium salt polymers, polyvinyl benzene
sulfonic acid, and the water-soluble salt of said acid, then
forming an electrophotographic sensitive layer on the
electroconductive layer so obtained. It is known that to provide
water resistance to paper generally involves the impregnation by a
water resistant binding agent and inorganic pigment particles, such
as, for example, clay or barium sulfate, resulting in a water
resistant paper which when immersed in an organic solvent, is found
not to substantially impede the penetration by organic solvents.
Further, such water resistant paper as above described has been
shown to provide insufficient electroconductivity and, therefore,
is found to be unsuitable without further modification as a base
paper for electrophotography. In order to improve the
electroconductivity of the base paper, a resin layer is provided
which overlies the water resistant layer. The water resistant layer
is usually composed of clay in combination with materials, such as,
starch, casein, styrene-butadiene copolymers or
butadiene-acrylester copolymers serving as a binding agent. Since
the aqueous solution of this resin possesses a high water
repellence, it cannot be applied to the base because it is repelled
very strongly. It is difficult to solve this problem by changing
the solvent since any resin having high electroconductivity is
sparingly soluble in organic solvents and, therefore, can only be
dissolved using water so that a surface active agent may be
employed to subdue or eliminate this repellence. Since the pigment
layer is porous, the solution as spread is found to penetrate into
the pigment layer more quickly and as a consequence thereof a
laterally continuous film cannot be formed. Consequently, when an
electrophotographic layer is formed thereon, there is observed a
heavy deposition of toner particles in the areas of low charged
density.
Without resorting to constant adjustment as hereinbefore mentioned
the system of the present invention contemplates employing a water
type inorganic colloidal solution which when applied to a smooth
water resistant layer may be spread thereon without being repelled
at all and is able to fill voids present in the porous structure
conferring strong hydrophillic properties to the surface thereof.
The aqueous solution of the resin to be employed having a high
electroconductivity may be spread uniformly without resort to the
use of a surface active agent. It is found that the film formed
upon drying is perfectly continuous in the lateral direction.
Although it is seen that a two step treatment is involved, the
conductive paper base obtained as a result of the treatment has
been found to have a smoothness equal to a plastic film covered by
a layer of vacuum deposited metal and, consequently, may serve as
an ideal base in the reproduction of continuous tone images.
Although any suitable inorganic colloidal solution may be employed
in the system of the present invention, colloidal silica and
colloidal alumina are preferred. Of these two, colloidal alumina is
found to form a film having a higher degree of electroconductivity
than the silica film in a wide range of humidity conditions. It is,
therefore, more desirable to employ colloidal alumina in an
environment where there is a requirement for a base of particularly
low resistance. Water dispersions of both colloidal alumina and
colloidal silica are commercially available. If desired, a small
quantity of film forming substance may be added to the colloidal
dispersion. However, it is preferred to control the addition of any
such film forming substance to a maximum of up to about 30% by
weight of the inorganic colloidal dispersion. The film forming
substance so added may be in the form of a water emulsion of a
water-insoluble resin or of a resin which becomes insoluble upon
hardening. Since colloidal silica offers a higher degree of
colloidal stability, it is found to permit the incorporation of
many substances without disturbing the dispersion. In the case of
colloidal alumina, on the other hand, it is found desirable to
employ the substance by itself. The colloid may be employed in a
concentration of about 0.1 grams (g) to 3 g per meter squared
(M.sup.2) of the area covered and preferably from about 0.2 g to
about 1.5 g per M.sup.2. It is found in the case where the
inorganic colloid is employed alone that a coating of excessive
thickness is undesirable because the colloidal layer tends to form
cracks and in subsequent coatings tends to become brittle and
break.
In the normal course of manufacture, a binding agent is not added
to the inorganic colloidal layer since no advantage is gained by
the addition thereof. Such binding agents are normally preferred to
be and are found to be water insoluble so that no particular
advantages are obtained since the subsequent application of an
electroconductive layer is accomplished normally with water. It is,
therefore, found to be more desirable to use the colloidal
solution, for example, colloidal silica or colloidal alumina by
itself.
When colloidal silica is spread at a rate of about 1 g per M.sup.2
on the surface of a machine coat paper, the surface resistance upon
drying is found to have a resistance of about 5 .times. 10.sup. 9
ohms per square in an atmosphere of about 40 percent relative
humidity. A coating of colloidal alumina spread at about the same
concentration results in a surface resistance having a value
decreased by a power of 100. It is permissible to incorporate into
the inorganic colloidal layer a hydroscopic inorganic salt or a
hydroscopic polyhydro compound. However, in the case of colloidal
alumina dispersions an electroconductive layer is obtained having
highly desirable properties so that it is not necessary to
incorporate such additives. Therefore, alumina dispersions are
generally preferred.
The surface of the inorganic colloidal dispersions obtained are
found to be highly hydrophillic and, therefore, is highly desirable
for use in connection with an aqueous solution to be spread
thereover. The electroconductive layer applied thereover is
accomplished with facility because it is a hydrophillic resinous
layer. Any suitable hydrophillic resinous layer may be employed to
provide the desired electroconductivity. Cationic polymers obtained
from monomers incorporated in the quaternary ammonium salt,
polyvinyl benzene sulfonic acid and salts thereof, and sulfonates
of polystyrene are preferred resins because they possess a high
degree of electroconductivity over a wide range of humidities and
form ideal surfaces capable of completely preventing permeation of
organic solvents. In addition, where a pretreatment is made such as
with alumina colloid, the resin solution is found to be spread
easily on the surface without being repelled and does not permeate
excessively into the porous layer of the surface, but results in a
laterally continuous film. The film of resinous material so applied
is spread in a concentration of from about 1 g to about 4 g per
M.sup.2. Polyvinyl benzene potassium sulfonate is a preferred resin
because it forms a film more resistant to permeation of solvent
than cationic polymer resins. The electroconductive resin layer may
also contain a polyhydric alcohol, a hygroscopic inorganic salt, a
miscible resin having a still higher resistance, and still other
components. Polyvinyl alcohol is particularly inexpensive and
provides a satisfactory film and, therefore, is preferred for use
over other additives. Since the addition of large quantities of
substances, such as, polyvinyl alcohol which has a relatively low
electroconductivity results in a degraded electroconductivity at
lower humidities it is desirable to avoid the addition of such
quantities.
The general nature of the invention having been set forth, the
invention will now be described illustratively in terms of the
following specification and the drawings in which:
FIG. 1 illustrates one embodiment of the electrophotographic
sensitive paper produced in accordance with the system of the
present invention.
FIG. 2 represents the same structure as seen in FIG. 1 with the
exception that an extremely thin insulating barrier 21 has been
added.
FIG. 3 represents the structure as illustrated in FIG. 1 with the
exception that a highly electroconductive carbon layer has been
provided.
In FIG. 1 is seen one embodiment of the electrophotographic
sensitive paper of the present invention, wherein the paper base 1
has coated thereover a clay layer 2 which may comprise a baryta
layer or a machine coat layer or the like having located thereover
a film composed mainly of colloidal silica or colloidal alumina 3
having coated thereover an electroconductive water soluble resinous
layer 4, and finally, having coated thereover an electroconductive
sensitive layer 5. Layer 6 underlying the fibrous paper layer 1 is
included to illustrate the application of a curl-balancing layer
which may be employed when desired. When so employed this layer is
selected so that it possess a high degree of
electroconductivity.
In FIG. 2 is seen the structure as illustrated in FIG. 1 with the
exception that an extremely thin insulative barrier layer 21 is
provided between layers 4 and 5. This layer is hardended and
designed so as not to be dissolved by the solvent which is used in
coating the sensitive layer 5.
In FIG. 3 is seen a structure as illustrated in FIG. 1 with the
exception that a highly electroconductive carbon layer 31 is
provided below layer 2, the black color of the carbon layer being
completely masked by layer 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To further define the specifics of the present invention the
following examples are intended to illustrate and not limit the
particulars of the present system. Parts and percentages are by
weight unless otherwise indicated.
EXAMPLE I
A black electroconductive paint comprising a water emulsion of
vinyl acetate resin and carbon black is spread on the non-art
surface of a one face art paper having a thickness of about 90
microns. To the art surface of a portion of this paper is applied
about a 10 percent aqueous solution of polyvinyl benzene potassium
sulfonate resulting in the appearance of small spot-shaped beads
repelled by the surface indicating that the solution may not be
spread uniformly thereover. To another portion of the paper the
same solution is coated with the addition of a small quantity of
surface active agent resulting in greatly improved wettability.
However, it is found that the film after drying has no luster
indicating that the solution has penetrated into the clay layer. To
a third portion of this paper a water dispersion containing
colloidal alumina at about 5 percent by weight is spread to a
concentration of about 0.5 g per M.sup.2 on the art layer and then
dried. Over this is spread the 10 percent aqueous solution of
polyvinyl benzene potassium sulfonate as previously used resulting
in an extremely smooth uniform film. An electrophotographic
sensitive layer comprising zinc oxide and an alkyd resin is spread
with toluene over the polyvinyl benzene potassium sulfonate layer
over portions of the paper both treated and not treated with the
colloidal alumina. The material is then dried and adapted to
darkness. When both portions of the paper are charged and exposed
utilizing methods as hereinbefore described and developed employing
a liquid developing agent, it is found that on the treated paper
the uniformity of density in the low density area is very good
wherein in the case of the untreated paper, uneven density is
conspicuously present in the low density areas.
EXAMPLE II
A water dispersion of colloidal alumina is spread to a
concentration of about 1 g per M.sup.2 on both surfaces of a two
surface art paper having a thickness of about 100 microns. Calgon
Conductive Polymer 261, a 40 percent aqueous solution of a
conductive polymer having the formula: ##SPC1##
is diluted with water and applied to only one side of the surfaces
resulting in an extremely smooth surface. To this is applied an
electrophotographic layer similar to that as described in Example
I. When the paper is imaged as in Example I, an excellent
reproduction of a continuous tone image is obtained.
EXAMPLE III
The same procedure as outlined in Example I is performed with the
exception that colloidal silica is used in place of colloidal
alumina and the electroconductive layer comprising polyvinyl
benzene potassium sulfonate is substituted by a film comprising
about 10 parts of polyvinyl benzene potassium sulfonate and about
10 parts of glycerin. When this paper is imaged as in Example I, an
excellent continuous tone image is obtained.
EXAMPLE IV
The method as outlined in Example II is performed with the
exception that the colloidal alumina is substituted by a mixture of
8 parts of colloidal silica with about 2 parts of polyvinyl
alcohol. When employed in an imaging process as in Example I there
is obtained an excellent continuous tone image.
EXAMPLE V
An electrophotographic paper is provided as in Example I with the
exception that an insulative layer having the thickness of about 1
micron comprising a mixture of styrene-maleic anhydride copolymer
with epoxy resin is formed on the electroconductive layer of
polyvinyl benzene potassium sulfonate prior to the formation of the
electrophotographic sensitive layer, heated at about 80.degree.C
for about 1 hour and then coated with the sensitive layer. When
this paper is imaged utilizing techniques similar to those as
employed in Example I, an excellent reproduction of a continuous
tone image is obtained.
EXAMPLE VI
A layer comprising gelatin and carbon black is applied to one
surface of paper. Over this layer is applied a baryta layer such as
that generally employed in photographic printing paper. This paper
is then treated as in Example I with a colloidal dispersion and
then coated as in Example I with an electroconductive layer and
then finally with an electrophotographic sensitive layer. This
electrophotographic sensitive paper when imaged as in Example I
results in an extremely high quality reproduction when liquid
development is employed.
EXAMPLE VII
A solution comprising about 10 parts alumina sol, and 90 parts
methanol is spread on the art layer of a one surface art paper
having a weight of about 1 to 30 g per M.sup.2 so that upon drying
the weight of the coating is found to be about 2 g per M.sup.2.
About a 10 percent aqueous solution of polyvinyl benzene potassium
sulfonate is spread thereover forming an extremely smooth film.
Over this electroconductive layer an electrophotographic sensitive
layer similar to that of Example I is formed. When imaged employing
techniques as employed in Example I, an excellent reproduction of a
continuous tone image is obtained.
Although the present examples were specific in terms of conditions
and materials used, any of the above listed typical materials may
be substituted when suitable in the above examples with similar
results. In addition to the steps used to carry out the process of
the present invention, other steps or modifications may be used if
desirable. For example, other layers may be employed to the
non-imaging surface of the electrophotographic paper to desirably
adjust colloidal properties. In addition, other materials may be
incorporated in the system of the present invention which will
enhance, synergize or otherwise desirably affect the properties of
the systems for their present use. For example, other layers
employed on the imaging surface may also be applied to the
underside or non-image surface of the paper as desired.
Anyone skilled in the art will have other modifications occur to
him based on the teachings of the present invention. These
modifications are intended to be encompassed within the scope of
this invention.
* * * * *