U.S. patent number 3,850,830 [Application Number 05/306,242] was granted by the patent office on 1974-11-26 for liquid developer containing extender body particles.
Invention is credited to Osamu Fukushima, Masamichi Sato, Yasuo Tamai.
United States Patent |
3,850,830 |
Fukushima , et al. |
November 26, 1974 |
LIQUID DEVELOPER CONTAINING EXTENDER BODY PARTICLES
Abstract
Developed images with substantially no fogging in the background
areas or streaking in the image areas are obtained in a liquid
development system employing a liquid developer comprising an
insulating liquid vehicle having dispersed therein charged toner
particles and charged extender body pigment particles selected from
the group consisting of calcium carbonate, aluminum hydroxide,
barium sulfate, aluminum oxide, talc, silica, calcium silicate,
magnesium carbonate, magnesium oxide and mixtures thereof.
Inventors: |
Fukushima; Osamu (Asaka-shi,
Saitama-ken, JA), Sato; Masamichi (Asaka-shi,
Saitama-ken, JA), Tamai; Yasuo (Asaka-shi,
Saitama-ken, JA) |
Family
ID: |
26789401 |
Appl.
No.: |
05/306,242 |
Filed: |
November 13, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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94967 |
Dec 3, 1970 |
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Current U.S.
Class: |
430/114;
430/115 |
Current CPC
Class: |
G03G
9/135 (20130101); G03G 9/12 (20130101) |
Current International
Class: |
G03G
9/135 (20060101); G03G 9/12 (20060101); G03g
009/04 () |
Field of
Search: |
;252/62.1 ;106/15FP
;117/137 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Smith; Ronald H.
Assistant Examiner: Brammer; J. P.
Parent Case Text
This is a continuation of application Ser. No. 94,967, filed Dec.
3, 1970, now abandoned.
Claims
We claim:
1. An electrostatographic liquid developer comprising an insulating
liquid vehicle having a volume resistivity greater than about
10.sup.10 ohm-cm and dispersed therein charged colored toner
particles and white extender body pigment particles selected from
the group consisting of calcium carbonate, aluminum hydroxide, and
mixtures thereof; said extender body pigment particles being
present in from about one tenth to about ten times the amount of
the charged colored toner particles and having a particle size of
from about 0.01 to about 5 microns, said toner particles having a
size of from about 0.01 to about 1 micron; said extender body
pigment particles having a positive charge, both said charged toner
particles and said charged body pigment particles being capable of
being simultaneously deposited from said liquid developer in
response to a charge of opposite polarity on the latent image areas
of an imaging surface and said charged body pigment particles being
capable of preferential deposition in the background portions of
said imaging surface.
2. The liquid developer of claim 1 wherein said extender body
pigment particles are present in from about one quarter to twice
the amount of the charged toner particles.
3. The liquid developer according to claim 1 wherein said body
pigment particles are calcium carbonate.
4. The liquid developer according to claim 1 wherein said body
pigment particles are aluminum hydroxide.
5. The liquid developer of claim 1 wherein said extender body
pigment particles have a refractive index less than about 1.75.
6. The liquid developer of claim 1 wherein said extender body
pigment particles have a charge and suspension stabilizing resin
absorbed on the surface.
Description
BACKGROUND OF THE INVENTION
This invention relates to imaging systems and more particularly to
liquid development systems for developing electrostatic latent
images.
The formation and development of images on the surface of
photoconductor material by electrostatic means is well known. The
basic electrostatographic process as taught by C. F. Carlson in
U.S. Pat. No. 2,297,691 involves placing a uniform electrostatic
charge on a photoconductive insulating layer exposing the layer to
a light and shadow image to dissipate the charge on the areas of
the layer exposed to the light and developing the resulting
electrostatic latent image by depositing on the image a finely
divided electroscopic marking material referred to in the art as
"toner." The toner will normally be attracted to those areas of the
layer which retain a charge thereby forming a toner image
corresponding to the electrostatic latent image. The powder image
may then be transferred to a support surface such as paper and
permanently affixed to the support by any suitable means such as
heat fixing or solvent fixing. Alternatively, the powder image may
be fixed to the photoconductive layer if elimination of the powder
transfer step is desired. In addition, instead of latent image
formation by uniform charging and followed by imagewise exposure,
the latent image may be formed by directly charging the layer in
image configuration. Other methods are known for applying
electroscopic particles to the imaging surface. Included within
this group are the "cascade" development technique disclosed by E.
N. Wise in U.S. Pat. No. 2,618,552; the powder cloud development
technique disclosed by C. F. Carlson in U.S. Pat. No. 2,221,776;
and the magnetic brush process disclosed for example, in U.S. Pat.
No. 2,874,063.
Development of an electrostatic latent image may also be achieved
with liquid rather than dry developer materials. In conventional
liquid development, more commonly referred to as electrophoretic
development, an insulating liquid vehicle having finely divided
solid material dispersed therein contacts the imaging surface in
both charged and uncharged areas. Under the influence of the
electric field associated with a charged image pattern the
suspended particles migrate toward the charged portions of the
imaging surface separating out of the insulating liquid. This
electrophoretic migration of charged particles results in the
deposition of the charged particles on the imaging surface in image
configuration. Electrophoretic development of an electrostatic
latent image may, for example, be obtained by pouring the developer
over the image bearing surface, by immersing the imaging surface in
a pool of the developer or by presenting the liquid developer on a
smooth surface roller and moving the roller against the imaging
surface. The liquid development technique has been shown to provide
developed images of excellent quality and to provide particular
advantages over other development methods in offering ease in
handling. Liquid development systems also capable of providing high
development speed, the development speed of commercial embodiments
having recently reached a level of as high as about 10 centimeters
per second. However, with the currently available liquid
development systems, this development speed is practical only for
line copy since the development of continuous tone or halftone
images generally requires a much slower speed.
The liquid developers generally employed in these
electrophotographic imaging processes comprises fine electrically
charged particles suspended in an electrically insulating liquid.
In addition to the charged particles which are generally referred
to as toner, it is common to disperse or dissolve a charge
controlling agent to regulate the electric charge on toner
particles and a dispersing agent to obtain a stable dispersion.
A typical liquid developer employed in the production of black
developed images comprises carbon black particles suspended in a
liquid such as the highly insulating nonpolar organic solvents
including mineral oil, benzene, heptane, cyclohexane and decylene.
Typically, charge controlling agents including various resins,
varnishes, nondrying oils and wetting agents may be added to
provide the necessary control of charge on the toner particles.
While capable of forming satisfactory images, these liquid
developers exhibit various shortcomings when employed in automatic
machine configurations.
Specifically, difficulties are frequently encountered due to the
phenomenon of fogging. Fogging occurs when, for example, a
photoconductive insulating layer is charged and exposed to a light
and shadow pattern. In the background or nonimage areas, during
exposure, light renders the photoconductive layer conductive and
dissipates the charge. However, in these background or nonimage
areas when subjecting the photoconductive insulating layer to even
the strongest irradiation, a small electric charge persists in the
nonimage or background areas. This small charge attracts a small
amount of toner giving rise to fogging in the background areas of
the developed print.
In addition, prior liquid developers may result in the formation of
streaks on the image. Thus, when bringing an electrostatographic
imaging surface bearing an electrostatic latent image into contact
with liquid developer, a relative speed component is present
between imaging surface and the liquid developer. Streaks are
formed on the imaging surface in the high density portions of the
image along the direction of movement of developer relative to the
imaging surface.
Furthermore, prior development systems employing a roller developer
dispensing device, have resulted in the formation of apparatus
stains due to the friction between the rollers and the surface
holding the electrostatic latent image. For example, in processes
in which the liquid developer is supplied between the surface
bearing the electrostatic latent image and a metal roller which
functions as the developing electrode and is rolled across the
imaging surface, or in imaging systems in which an
electrophotographic material passes between a pair of pinch rollers
while the liquid developer is supplied between the roller and the
surface bearing the latent image staining of the apparatus may
occur. This occurs since the metal rollers are kept in direct
contact with the imaging surface, and any minute projecting
portions present on the imaging surface are scraped by the metal
roller permitting toner to be collected thereby forming stains.
Furthermore, the prior liquid developers are incapable of producing
image tone such as that obtainable in silver halide photographic
paper.
SUMMARY OF THE INVENTION
It is therefore an object of this invention to provide a liquid
development system which overcomes the above noted
deficiencies.
It is another object of this invention to provide a liquid
developer which produces high density, nonstreaky developed
images.
It is another object of this invention to provide a liquid
development system which produces developed images with
substantially no fogging.
It is another object of this invention to provide a liquid
development system which is capable of producing fine grain smooth
appearance developed images.
It is another object of this invention to provide a liquid
development system capable of producing developed images having a
tone resembling the appearance obtained with silver halide
photographic paper.
The above objects and others are accomplished, generally speaking,
by providing an electrostatographic imaging system of the liquid
development type wherein a liquid developer comprising an
insulating liquid vehicle, charged colored particles and extender
body pigment particles charged to the same polarity as the charged
colored particles is employed. In addition, if necessary, charge
controlling agents, dispersion stabilizing agents, fixing agents
and other well known materials may be suspended or dissolved in the
liquid developer. Alternatively, the charge control agents, the
dispersion stabilizing agents and fixing agents may be coated on
the individual charged particles.
Any suitable extender body pigment particle may be employed in the
practice of the present invention. By the term extender body
pigment is intended to define that group of finely divided
materials which will provide a color the same as or similar to the
background areas of the final print surface such as either a
photosensitive paper such as "Electrofax" paper or ordinary paper.
In the most practical of operations, therefore, the body pigment
particles will be substantially white since most commercial imaging
processes produce prints of black image areas on white background
areas. It is, however, to be understood that if background areas of
other colors are desired appropriately colored pigments of the
background areas may also be employed. Typically, when employing
body pigment particles in an electrostatographic imaging system
providing finished copy with white background and dark color image
areas, pigments with refractive indices not greater than 1.75 may
be employed. Typical specific materials include calcium carbonate,
aluminum hydroxide, barium sulfate, aluminum oxide, talc, silica,
calcium silicate, magnesium carbonate and magnesium oxide. It is
essential that the body pigment particles do not either discolor or
decompose the tone particles.
The body pigment particles employed in the practice of the present
invention may be of any suitable size. Typically, the body pigment
particles are within the range of from several tens of times to
several tenths of the diameter of the color charged or toner
particles. To provide uniformity of suspension in the liquid
developer and deposition, it is preferred, however, to maintain the
size of the body pigment particles within a range of several times
larger to several times smaller than the toner particles.
Typically, the extender pigment is of a particle size of from about
0.01 to about 5 microns. The toners employed in the practice of
this invention may be of any suitable size. Typically, the toner
particles do not have an average particle size exceeding about 1
micron or less than about 0.01 micron. Thus, the extender body
pigment particles will generally be of about the same size as toner
particles. Generally the number of extender body pigment particles
may be employed in an amount within the range of from about one
tenth to about ten times the amount of the charged toner particles
present in the liquid developer. However, to avoid the deposition
of undue quantities of extender body pigment particles in the image
areas, it is generally preferred that the extender body pigment
particles be present in an amount within the range of from about
one quarter to about twice the amount of the charged toner
particles. Optimum image density in the image areas together with
substantially complete reduction of fogging in the nonimage or
background areas, it is generally achieved when the number of
extender body pigment particles is about the same amount as that of
the charged toner particle.
The liquid developer of the present invention may be prepared in
any suitable manner. Typically, the liquid developer may be
prepared by mixing the several constituents of the developer
together. It may also be prepared by mixing a first liquid portion
containing the toner particles with an insulating liquid and a
second portion containing the body pigment particles.
Alternatively, a paste containing toner and body pigment particles
may be dispersed within the insulating liquid.
From the above description of the invention, the choice of specific
materials and operating conditions is deemed to be well within the
scope of those skilled in the art and therefore the scope of the
invention is not limited by the hereinabove mentioned illustrative
materials. The extender body pigment particles may be employed with
any suitable liquid developer. Typical liquid developers contain
liquids of relatively high insulating value generally having a
volume resistivity greater than about 10.sup.10 ohm-cm so as not to
effect the electrostatic charge pattern on the insulating layer and
low dielectric constants of less than about 3.4. Typical specific
vehicles include hydrocarbons such as benzene, xylene, hexane,
naptha, kerosene, halogenated hydrocarbons such as carbon
tetrachloride, trichloroethylene and chloroform. Typical charged
toner particles which may be employed with the liquid developer
include, among others, charcoal, carbon black, magnesium oxide,
lithopone, cadmium yellow, chrome yellow, cobalt blue, cadmium red,
burnt siena, Hansa yellow, rose bengal and phthalocyanine.
Typically, the charged toner particles are present in the liquid
developer in an amount of from about 2 to about 20 grams per liter,
and are conventionally dispersed and suspended in the liquid by
stirring or agitation. Where a highly uniform stable suspension is
desired, this suspension may be passed through a colloid mill. The
liquid developers according to the present invention may be
employed to develop electrostatic charge patterns present on any
suitable imaging surface. Basically, any material capable of
holding a charge pattern may be employed. Typical materials include
dielectric layers, xeroprinting masters and photoconductors. A
particularly preferred material for use in automatic copying
machines is a photosensitive paper comprising photoconductive
pigment particles in an insulating binding layer. Typically, this
paper comprises zinc oxide photoconductive particles present in an
insulating binding layer which is overcoated on a paper substrate.
The choice of particular imaging member and particular development
technique may be readily determined by one skilled in the art. For
example, the photosensitive paper described above may be
substituted with photoconductor materials made from cadmium
sulfide, zinc sulfide, zinc selenide, cadmium selenide, titanium
dioxide, phthalocyanine and polyvinyl carbazole. As previously
discussed, the liquid developers according to the present invention
may also contain dispersed in the insulating liquid vehicle charge
control agents and suspending agents for their well known
functions. The selection of the appropriate materials to perform
these well known functions may be readily made by the artisan.
When employing a liquid developer comprising toner particles which
are positively charged, the extender body pigment particles must
also be positively charged in the insulating liquid. The use of
calcium carbonate and aluminum hydroxide as the extender body
pigment particles is particularly preferred when positively charged
particles are to be employed since they become positively charged
merely be being suspended in the insulating liquid. In order to
disperse these minute particles to provide a stable suspension in
the insulating liquid a resin may also be employed. Typically, from
about 0.5 to about 50 parts by weight of the resin per part of the
extender pigment may be employed. A portion of this resin appears
to be strongly absorbed on the surface of the calcium carbonate or
the aluminum hydroxide and the charge on these particles may be
further stabilized depending on the specific resin employed.
Typically, from about 2% to about 30% by weight of the total resin
is absorbed on the surface of the extender pigment. A particularly
preferred resin providing maximum stabilization of charge and
suspension is a rosin modified phenol formaldehyde resin heated
with linseed oil.
While the above explanation has been made principally with regard
to toner particles carrying a positive charge, it is to be
understood that the present invention also encompasses liquid
developers containing toner particles which have been provided with
a negative charge. Liquid developers containing negatively charged
toner particles may be employed to develop positively charged image
patterns. They may also be used as reversal developers. In both
instances, the liquid developers may have extender body pigments
added which are capable of being negatively charged. It has been
observed that the liquid developer will exhibit the behavior of a
negative toner when the amount of negatively charged toner
particles present in the liquid developer is larger than that of
the positively charged body pigment particles. Conversely, the
developer will exhibit the behavior of a positive toner when the
amount of positively charged extender pigment is greater than the
negatively charged toner particles. This occurs since the
negatively charged toner particles are encircled by the extender
particles so the toner particles behave as positive toners.
It is possible to maintain the negative polarity charge of the
liquid developer by the use of a charge controlling agent. Any
suitable charge controlling agent may be employed. A typical
material for controlling the charge is lecitin. It is also possible
to provide the body pigment particles with a negative charge by
coating the particles with a thin layer of a resin which is soluble
in the carrier liquid. Any suitable resin may be employed for this
purpose. Typical materials include polyvinyl chloride and
copolymers containing vinyl chloride and nitrocellulose.
The liquid developer of the present invention when employed as an
electrophoretic liquid developer is capable of producing images
which are essentially, completely free from background fogging. In
addition, the developer of this invention provides images of clear
tone resembling the appearance of silver halide photographic paper.
Furthermore, the liquid developer according to this invention,
provides a very fine grain developed toner image. In addition, the
absence of stain resulting from friction between the developer
applicator roller and the imaging surface wherein a roller
developing method is employed is substantially completely
eliminated.
While the exact mechanism and reasons for the improved results are
not fully understood at the current time, it is presently believed
that the development of images which are substantially free from
background fogging is due to a preferential deposition of the
extender body pigment in the background portions of the imaging
surface which thereby prevent deposition and adherence of the toner
in these background portions. It is further believed that the clear
tone resembling the appearance of silver halide reproductions is
due to the fact that the extender body pigment particles and the
toner particles are deposited together and thereby increase the
transparency of the toner image. The fact that finer grain toner
images are capable of being achieved with the liquid developer of
the present invention is believed attributable to the fact that
aggregates which consist exclusively of a toner material are
prevented since there is a simultaneous deposition of toner and
extender pigment in the image areas which tends to suppress the
formation of large aggregates which consist solely of colored toner
material. The absence of staining is further believed to be
attributed to the fact that the body pigment particles act as a
lubricant or to the preferential deposition of the body pigment
particles on the projecting portions of the imaging surface. The
ability to produce images which are substantially free from streaks
in a liquid development system of increased development speed has
not been satisfactorily explained. It has been established,
however, that with comparison of liquid developer according to the
present invention and developers containing resin particles instead
of extender body particles that increased development speed and the
above mentioned improved image qualities are achieved.
DESCRIPTION OF PREFERRED EMBODIMENTS
The following, nonlimiting examples further define, describe and
compare preferred materials, methods and techniques of the present
invention. Example II is presented for comparative purposes. Unless
otherwise specified, all amounts proportions and percentages are by
weight.
EXAMPLE I
A photosensitive paper comprising an electroconductive paper
substrate overcoated with a photoconductive layer of powdered zinc
oxide in an insulating resinous binder is charged and exposed to a
light and shadow pattern in conventional manner. The electrostatic
latent image formed on the zinc oxide sheet is developed by passing
the sheet through a bath of a liquid developer made according to
the following procedure:
Paste A is obtained by ball milling the following composition for 8
hours.
______________________________________ Carbon black 4000g (particle
size 0.05 - added ) Varnish obtained by heating a mixture of 5000g
equal amounts of rosin-modified phenol- formaldehyde resin and
linseed oil Linseed oil 1000g
______________________________________
Paste B is obtained by kneading the following composition on a
three roll kneader.
______________________________________ Aluminum hydroxide 2000g
(particle size 0.07 - 0.2.mu.) Varnish obtained by heating a
mixture of 4000g rosin-modified phenol-formaldehyde resin and
linseed oil Linseed oil 1000g
______________________________________
Both paste A and paste B contain particles having a charge of
positive polarity. The liquid developer is obtained by dispersing
20 grams of paste A and 15 grams of paste B into 10 liters of
"Decalin," decahydronapthalene available from E.I. duPont de
Nemours and Company. The developed image on the zinc oxide sheet is
substantially free of fogging in the background areas, is
substantially free of streaks in the image areas and has a
relatively fine grain image area. In addition, the tone achieved is
similar to that obtained with silver halide photographic paper.
EXAMPLE II
The procedure of Example I is repeated except that only 20 grams of
paste A is dispersed in 10 liters of "Decalin". The developed image
on zinc oxide paper has a high fogging level, streaky images and a
relatively coarse grain image. In addition, the tone is inferior to
that obtained in the silver halide photographic paper.
EXAMPLE III
The procedure of Example I is repeated except that the liquid
developer is made by dispersing 20 grams of paste A in 5 liters of
"Decalin" and 15 grams of paste B in 5 liters of "Decalin". When
mixed together in equal amounts a liquid developer is formed which
when employed to develop an electrostatic latent image formed in
the manner described in Example I produces prints of quality
similar to that obtained in Example I.
EXAMPLE IV
The procedure of Example I is repeated except that development of
the electrostatic latent image is accomplished with a liquid
developer made by blending the following composition in a ball mill
for one hour.
______________________________________ Phthalocyanine blue 400g
Polymerized linseed oil 500g Linseed oil-modified alkyd resin 500g
Aluminum hydroxide 200g Kerosene 300ml
______________________________________
Forty grams of this paste is then dispersed in 10 liters of
kerosene while under the influence of ultrasonic wave. The toner
has a stable positive charge in the carrier liquid. When used as a
liquid developer, in the manner described in Example I, an image
with substantially no fogging or streaking is obtained. In
addition, the image is more transparent than that obtained by means
of ordinary electrophotographic processing.
EXAMPLE V
The procedure of Example I is repeated with a liquid developer
prepared by blending the following composition in a ball mill for
one hour in the following manner.
______________________________________ Brilliant carmine 6B 250g
Polymerized linseed oil 250g Linseed oil-modified alkyd resin 300g
Precipitated barium sulfate 200g Kerosene 300ml
______________________________________
Thirty grams of this paste are dispersed while under the influence
of ultrasonic wave into a mixture of 8 liters of cyclohexane and 2
liters of kerosene to provide a liquid developer capable of
providing a red image. The precipitated barium sulfate is provided
with positive charge in the carrier liquid. Image quality similar
to that described in Example IV is achieved.
EXAMPLE VI
The procedure of Example I is repeated with the liquid developer
prepared by blending the following composition in a ball mill for
one hour.
______________________________________ Benzidine yellow 40g Varnish
(same as in Example I) 80g Linseed oil 60g Aluminum hydroxide 15g
Calcium carbonate 15g ______________________________________
Twenty grams of this paste are dispersed while under the influence
of ultrasonic wave into a mixture of 8 liters of cyclohexane and 2
liters of kerosene. The particles of benzidine yellow when employed
alone exhibit an unstable positive charge in the carrier liquid.
Calcium carbonate shows strong positive charge in the carrier
liquid and stabilized the positive charge on the benzidine yellow.
Image quality similar to that achieved in Example IV is observed
when the zinc oxide sheet is immersed in the liquid developer.
EXAMPLE VII
A photoconductive insulating layer comprising a paper substrate
with a coating thereon of zinc oxide photoconductive particles in
an insulating resinous binder is charged and exposed to a negative
image. The electrostatic latent image thus formed is developed with
a liquid developer prepared by blending the following composition
in a ball mill.
______________________________________ Calcium carbonate 250g Vinyl
chloride-vinyl acetate copolymer 125g Varnish obtained by heating
rosin-modified phenol-formaldehyde resin and linseed oil 400g Ethyl
acetate 3000ml ______________________________________
Thirty milliliters of the paste is dispersed while under the
influence of ultrasonic wave in a carrier liquid of the following
composition.
______________________________________ Cyclohexane 1500ml Kerosene
300ml Cottonseed oil 200ml
______________________________________
This developer contains negatively charged particles and is
substantially transparent in appearance.
A developer containing negatively charged green toner of the
following composition is prepared in the same manner.
______________________________________ Phthalocyanine green 5g
Polymerized linseed oil 25g Cyclohexane 1500ml Kerosene 475ml
______________________________________
One part by volume of the green developer and one part by volume of
the liquid developer containing the body pigment are mixed to
obtain liquid developer, in which the toner has a stable negative
charge. The negative electrostatic latent image formed on zinc
oxide photosensitive paper is developed with this liquid developer
to obtain a satisfactory reversal image. Streaking and fogging are
barely observed on the developed image.
Although particular embodiments have been set forth using the
development system and technique of this invention, these are
merely intended as illustrations of the present invention. There
are other systems and techniques which may be substituted for those
described. Other modifications of the present invention will occur
to those skilled in the art upon a reading of the present
disclosure which modifications are intended to be included within
the scope of this invention.
* * * * *