U.S. patent number 3,718,594 [Application Number 05/093,798] was granted by the patent office on 1973-02-27 for method of preparing magnetically responsive carrier particles.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Howard A. Miller.
United States Patent |
3,718,594 |
Miller |
February 27, 1973 |
METHOD OF PREPARING MAGNETICALLY RESPONSIVE CARRIER PARTICLES
Abstract
Ferromagnetic carrier particles having uniform surface and
triboelectric properties can be prepared by treatment of commercial
iron powders in an aqueous acid solution, followed by removal of
acid, rinsing and controlled drying to induce or exclude oxidation.
The resultant particles can subsequently be overcoated with a thin,
uniform, continuous film of a nonferrous material such as metal or
a resinous material. These carrier particles are useful for
applying electroscopic toner material to electrostatic latent
images.
Inventors: |
Miller; Howard A. (Rochester,
NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
22240791 |
Appl.
No.: |
05/093,798 |
Filed: |
November 30, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
799966 |
Feb 17, 1969 |
3632512 |
|
|
|
Current U.S.
Class: |
430/137.13;
234/3; 234/28; 427/216; 428/928; 430/111.34; 430/111.41; 234/25;
234/41; 428/570; 430/114 |
Current CPC
Class: |
G03G
9/1139 (20130101); G03G 9/1132 (20130101); G03G
9/1131 (20130101); G03G 9/1075 (20130101); Y10S
428/928 (20130101); Y10T 428/12181 (20150115) |
Current International
Class: |
G03G
9/107 (20060101); G03G 9/113 (20060101); G03g
009/02 () |
Field of
Search: |
;252/62.1
;117/17.5,234,235,49,1M,236,237,240,50 ;29/196.3,196.5,196.6,199
;134/28,25,3,41 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Pianalto; Bernard D.
Parent Case Text
This application is a division of U.S. Patent application Ser. No.
799,966, Method of Preparing MagneticaLly Responsive Carrier
Particles, filed Feb. 17, 1969 and now U.S. Pat. No. 3,632,512.
Claims
I claim:
1. A process for preparing magnetically responsive developer
compositions for use in the development of electrostatic charge
patterns comprising the steps of dispersing iron powder in a dilute
aqueous mineral acid bath having a concentration of about 1N to
about 3N, agitating the powder while in the bath to dissolve
metallic iron from said particles, separating the powder from the
bath, rinsing the powder with water containing an antioxidant to
inhibit oxidation of the acid-treated iron particles, drying the
powder at a temperature above the dew point of the ambient
atmosphere, overcoating the individual iron particles with a thin,
continuous layer of an electrically conducting nonferrous metal to
form an electrically conducting, magnetically responsive carrier
particle having an electrical resistance of less than about 10
ohms, and subsequently mixing from about 90 to about 99% by weight
of the resultant carrier particles without about 10 to about 1% by
weight of an electroscopic toner material having a article size
smaller than that of the carrier particles.
2. The process as described in claim 1 wherein up to about 2
percent by weight of the iron is dissolved from said particles.
3. A process as described in claim 1 wherein the antioxidant is
selected from the group consisting of hydrazine sulfate and sodium
nitrite.
4. A process as described in claim 1 including the additional step
of rinsing the wet powder with a water-miscible organic solvent to
remove residual water from the iron prior to drying the powder.
5. A process as described in claim 4 wherein the water-miscible
organic solvent is selected from the group consisting of acetone
and a lower alkyl alcohol.
6. A process for preparing a magnetically responsive developer
composition for use in developing electrostatic charge patterns
comprising the steps of dispersing iron powder in a dilute aqueous
mineral acid bath having a concentration of about 1N to about 3N,
agitating the powder while in the bath, separating the powder from
the bath, rinsing the powder with water containing an antioxidant
to inhibit oxidation of the iron, drying the powder in a
substantially oxygen-free atmosphere to form iron particles having
substantially no oxide on the surface thereof and having an
electrical resistance of less than about 50 ohms, overcoating the
individual iron particles with a thin, continuous layer of an
electrically conducting nonferrous metal to form an electrically
conducting, magnetically responsive carrier particle having an
electrical resistance of less than about 10 ohms, and subsequently
mixing from about 90 to about 99 percent by weight of the resultant
carrier particles with from about 10 to about 1 percent by weight
of an electroscopic toner material having a particle size smaller
than that of the carrier particles.
Description
This invention relates to electrophotography, and more
particularly, to magnetically attractable carrier particles useful
in the magnetic-brush type development of electrostatic latent
images.
Electrophotographic imaging processes and techniques have been
extensively described in both the patent and other literature, for
example, U. S. Pat. Nos. 2,221,776; 2,277,013; 2,297,691;
2,357,809; 2,551,582; 2,825,814; 2,833,648; 3,220,324; 3,220,831;
3,220,833 and many others. Generally, these processes have in
common the steps of employing a normally insulating photoconductive
element which is prepared to respond to imagewise exposure with
electromagnetic radiation by forming a latent electrostatic charge
image. The electrostatic latent image is then rendered visible by a
development step in which the charged surface of the
photoconductive element is brought into contact with a suitable
developer mix.
One method for applying the developer mix is by the well-known
magnetic brush process. Such a process can utilize apparatus of the
type described, for example, in U. S. Pat. No. 3,003,462 and often
comprises a nonmagnetic rotatably mounted cylinder having fixed
magnetic means mounted inside. The cylinder is arranged to rotate
so that part of the surface is immersed in or otherwise contacted
with a supply of developer mix. The granular mass comprising the
developer mix is magnetically attracted to the surface of the
cylinder. As the developer mix comes within the influence of the
field generated by the magnetic means within the cylinder, the
particles of the developer mix arrange themselves in bristle-like
formations resembling a brush. The bristle formations of developer
mix tend to conform to the lines of magnetic flux, standing erect
in the vicinity of the poles and lying substantially flat when said
mix is outside the environment of the magnetic poles. Within one
revolution the continuously rotating cylinder picks up developer
mix from a supply source and then returns part or all of this
material to the supply. This mode of operation assures that fresh
mix is always available to the surface of the photoconductive
element at its point of contact with the brush. In a typical
rotational cycle, the roller performs the successive steps of
developer mix pickup, brush formation, brush contact with the
photoconductive element, brush collapse and finally mix
release.
In magnetic-brush development of electrostatic images, the
developer is commonly a triboelectric mixture of fine toner powder
comprised of dyed or pigmented thermoplastic resin with coarser
carrier particles of a soft magnetic material such as "ground
chemical iron" (iron filings), reduced iron oxide particles or the
like. The conductivity of the ferromagnetic carrier particles which
form the "birstles" of a magnetic brush provides the effect of a
development electrode having a very close spacing to the surface of
the electrophotographic element being developed. By virtue of this
development electrode effect it is to some extent possible to
develop part of the tones in pictures and solid blacks as well as
line copy. This ability to obtain solid area development with
magnetic brush developing sometimes makes this mode of developing
advantageous where it is desired to copy materials other than
simple line copy. One difficulty with such counter-electrode
development is that the exposure latitude obtainable is limited.
Consequently, for certain applications, it is desirable to suppress
the counter-electrode effect in order to obtain improved exposure
latitude. One method of suppressing the counterelectrode effect is
to use a carrier material which has a high electrical
resistance.
Presently available commercial iron powders, however, are not at
all uniform in regard to the properties of conductivity and
resistivity. In general, the materials now available have too high
resistivity to give good solid area development and are too
conductive to entirely suppress the counter-electrode effect. One
reason for the lack of uniformity in the electrical properties is
that the particles carry surface dirt, such as grease, oil, and
other contaminants. It has been suggested in the prior art that
typical iron carrier particles can be treated with methanol,
isopropanol, and other alcohols to rid the iron of grease, oil,
etc. Iron so treated is generally referred to as "alcoholized
iron."
However, the prior art has not recognized the heterogeneous nature
of the intimate surface of the iron powders used in this art. In
addition, no recognition has been given to the resulting
complications in magnetic-brush processing which arise from using
some of the presently available materials. The extraneous surface
dirt found on the available iron particles is only part of the
problem. In addition to the dirt, the iron particles invariably
carry a non-uniform distribution of iron oxide and oftentimes
pyrites such as iron sulfide, as well as other iron compounds. When
materials of this type are used in conventional magnetic brushes,
the iron carrier is in continuous motion and the constant friction
of the particles against one another and against the various
mechanical parts gradually remove bits of this nonuniform surface
material. The attrition will, of course, vary from point to point
on an iron particle depending on the nature of the deposit, its
thickness, friability, adhesion to the underlying structure, and
the like. Thus, with the available carrier materials, a progressive
change occurs in the character of the iron surface during use.
Correspondingly, the nature of the admixed toner also changes as it
becomes contaminated with the fine particles which have separated
from the surface of the carrier.
Accordingly, there is a need for iron carriers which will present a
more nearly homogeneous surface and which will have stable
triboelectric and other properties even during continued use.
Furthermore, there is a need for iron carrier particles which will
enhance the counter-electrode effect and thus improve the
solid-area type development obtainable in magnetic brush
processing. Also, there is a need for iron carrier particles which
can repress the counter-electrode effect so that fringing
development will be induced with its accompanying improvement in
exposure latitude.
It is, therefore, an object of this invention to provide a new
simple economic process for preparing magnetically responsive iron
carrier particles having a homogeneous surface.
It is another object of this invention to provide a new process for
preparing magnetically responsive carrier particles which process
is adapted for forming particles of high surface conductivity or
low surface conductivity, as desired.
A further object of this invention is to provide new developing
compositions for use in magnetic brush development.
These and other objects and advantages are accomplished in
accordance with this invention by the treatment of iron powder with
an aqueous solution of acid followed by removal of residual acid
and waste products evolved with subsequent controlled drying of the
iron powder under preselected conditions of temperature, relative
humidity and ambient atmosphere. In addition, the dried powder can
be further treated by applying one or more thin continuous layers
of an additional nonferrous material.
The carrier materials which are suitable for treatment in
accordance with this invention include ferromagnetic materials such
as iron powder in various forms. The phrase "iron powder" as used
herein is meant to include a wide variety of particulate,
magnetically responsive material the surface of which can be
readily oxidized and includes material in such forms as reduced
iron oxide bits; particles produced by atomization of molten metal
and subsequent cooling of the droplets; particles produced by
grinding, milling, filing, turning, etc; as well as particles of
iron alloys having oxidizable iron on the surface thereof such as
stainless steel and iron alloys containing nickel and/or cobalt.
The ferromagnetic carrier particles used can vary in size and in
shape with useful results being obtained with average particle
sizes of from about 1,200 to about 40 microns. Particularly useful
results are obtained with average particle sizes from about 600 to
about 60 microns. The size of the carrier particles used will, of
course, depend upon several factors, such as the type of images
ultimately developed, the desired thickness of any subsequent
coatings, etc.
Commercially available iron powder is first subjected to an acid
treatment in accordance to this invention. This acid treatment can
be carried out using a dilute aqueous solution of the acid. A wide
variety of acids can be used such as sulfuric, hydrochloric,
nitric, and other mineral acids. Sulfuric acid is a preferred
material, by virtue of the fact that it is inexpensive, readily
available, and only slightly volatile. In addition, certain organic
acids, such as acetic acids, e.g., trichloroacetic acid, etc, are
also useful in certain applications. In general, the acid
concentrations which are useful can vary from about 1-normal to
about 3-normal. Higher or lower acid concentrations can sometimes
be useful because of the quantity of iron being treated, the
average particle size or other such variables. The step of acid
treatment of the iron particles is in no way restricted to any
particular method of applying the acid. For example, spraying,
percolation, and/or other means can conveniently be used to
accomplish the acid treatment step. One very convenient procedure
is to form a slurry of the iron powder in dilute acid for a period
of time which will vary with the nature and concentration of the
acid used, the agitation applied, the required degree of attack by
the acid, the particle size of the iron powder, as well as the
character and thickness of the surface material which is to be
removed. When using commercial iron powders of average size, from
about 100 microns to about 400 microns, it is generally sufficient
to agitate the iron powder in a 5 percent aqueous solution of, for
example, sulfuric acid for about one minute at about
25.degree.C.
If necessary to stop the reaction of the acid on the carrier
powder, an alkaline solution can be added to the acid slurry.
Alternatively, the reaction can be checked by dilution with cold
water. However, it is generally simpler and more efficient to start
with an acid concentration of the appropriate value such that the
reaction rate will be sufficiently slowed down at the end of the
treatment period, so as to facilitate settling of the iron powder
and removal of the supernatant liquid. As mentioned above, the acid
concentration required will vary with different iron powders,
depending on the amount used and the average particle size, the
nature of the surface on the starting material, etc.
Despite the harmful effects of the various surface contaminants
found on commercial iron powders, such contaminants constitute only
a very small fraction of the total weight of the powder. In most
cases, the reduction in weight resulting from removal of undesired
surface contaminants and incidental solution of elementary iron in
the treatment of commercial iron powders by the method of this
invention, is of the order of about 1 to about 2 percent by weight
or less. Treatment need not be extended beyond the degree necessary
to remove the heterogeneous surface contaminants. No further
reduction in surface contaminants nor improvement in surface
uniformity is observed by continuing treatment until the loss of
metallic iron is about 2 percent by weight. Preferably, the
metallic iron lost by dissolution should be less than about 1
percent by weight of the iron powder. In fact, unduly prolonged
treatment not only results in needless consumption of acid and
dissolution of iron but, in some instances, can produce deleterious
results, by exposing occluded particles of acid-insoluble
material.
After processing the iron powder in the aqueous acid solution, the
acid is removed and the iron is washed by percolation or other
means to insure removal of any residual acid. A large part of the
material removed from the surface of the powder is often insoluble
and consequently, decantation washing is a preferred method of
eliminating both the residual acid and the suspended products of
the reaction. A simple decantation procedure can be carried out by
slurrying the iron in clean cold waTer followed by a settling
period to permit the iron particles of suitable carrier size to
settle to the bottom of the liquid. After settling the supernatant
liquid is rapidly decanted such that the unwanted contaminants are
carried off with the liquid. This washing operation can be repeated
until the rinse water is clear or until an established level of
residual turbidity is reached.
The process of this invention can be used to prepare iron particles
having very high surface conductivity. The highly conductive
particles, made in accordance with this invention, show surface
resistance values several orders of magnitude lower than the best
of the commercially available iron powders when measured in
magnetic brush conformation under standardized testing conditions.
For purposes of comparison, the resistance of the carrier particles
is measured in a standard resistance test. This test is conducted
each time using a 15 g. quantity of carrier material. A
cylindrically shaped magnet having a circular end of about 6.25
square centimeters in area is used to attract the carrier and hold
it in the form of a brush. After formation of the brush, the bar
magnet is then positioned with the brush-carrying end approximately
parallel to and about 0.5 cm. from a burnished copper plate. The
resistance of the particles in the magnetic brush is then measured
between the magnet and the copper plate. In general, the uncoated
conductive particles made in accordance with this invention have a
resistance of less than about 50 ohms, with especially preferred
materials having a resistance of less than about 20 ohms.
Metallic iron is a very good electrical conductor and the clean
elemental iron surface of the carrier iron prepared by this process
of this invention results in a highly conductive iron powder as
mentioned above. However, iron is also a highly reactive metal and
readily oxidizes in air. Therefore, it is of utmost importance when
making highly conductive carrier material by this invention to
repress oxidation during the washing and drying steps as well as
during subsequent storage. The repression of oxidation can be
accomplished in any of several ways. One useful way to repress
oxidation is by the addition of an antioxidant or reducing agent to
the wash water and particularly to the last several quantities of
wash water. A variety of known antioxidants or reducing agents can
be used to inhibit oxidation in the subsequent drying operation.
For example, one-half percent of hydrazine sulfate or sodium
nitrite is usually quite effective for this purpose. Oxidation can
also be minimized by the use of one or a succession of rinses in a
water-miscible organic solvent such as acetone or a lower alcohol
like methanol, ethanol and isopropanol. Such solvents remove the
residual water from the iron and speed subsequent drying.
Additionally, the temperature and relative humidity of the drying
air should also be carefully controlled. One reason for the careful
control is that warming of the iron powder will encourage oxidation
while similarly, if the iron is cooled too rapidly such that the
temperature drops below the dew point, condensation of water on the
iron will also encourage surface oxidation. Thus, when preparing
conductive carriers, it is necessary that drying be carried out
under temperature and relative humidity conditions which discourage
the formation of surface oxide.
In general, the iron powder processed according to this highly
conductive embodiment of the invention can be dried by agitating
continuously in a current of warm air. Generally, the temperature
of the air is in the range of from about 15.degree. to about
40.degree. C with a preferred temperature of from about 20.degree.
to about 30.degree.C. In addition, the drying temperature should be
kept above the dew point of the ambient atmosphere to avoid
unnecessary condensation. Furthermore, the relative humidity of the
drying air should be kept low. Generally, good results can be
obtained with relative humidity values of less than about 20
percent and preferably the relative humidity is less than about 20
percent. Under these conditions of temperature and humidity, the
resulting powder shows very high surface conductivity. If, however,
even higher surface conductivities are required, the iron can be
dried in an inert, substantially oxygen-free atmosphere such as
hydrogen, nitrogen, etc. After drying, the iron must be protected
from oxidation until ready for use. This can be readily
accomplished by storing it in an inert atmosphere in a sealed
container. When used, the carrier particles are mixed with a toner
material of suitable triboelectric properties which toner provides
a physical coating that effectively lessens any further oxidation
on the carrier during use. As a result, it is possible to maintain
the improved surface conductivity of the carriers of the invention
during extended periods of use in magnetic brush apparatus.
Of course, it is also possible to stabilize the improved surface
conductivity of particles prepared in accordance with this
invention by additional surface treatment of the carrier. One
particularly useful surface treatment involves overcoating each
carrier particle with a thin continuous layer of a nonferrous
electrically conducting metal which is more resistant to aerial
oxidation than iron. The materials useful for coating or plating
onto the present conductive carriers are typically nonferrous
metals which are substantially more resistant to surface oxidation
than iron and iron-alloys. Suitable coating materials having a
resistance to aerial oxidation greater than that of iron include
those metals in groups VIa, VIII, Ib and IIb of the Periodic Table
(Cotton and Wilkinson, Advanced Inorganic Chemistry, 1962, page
30). Particularly useful metals are cadmium, chromium, copper,
gold, nickel, silver, zinc, and the platinum group elements which
include ruthenium, rhodium, palladium, osimum, iridium and platinum
as well as mixtures or alloys of any of these. Most of these metals
are more electronegative than the iron starting material which
property is advantageous in certain coating procedures. With other
coating procedures, the metals more electropositive than iron can
be useful such as chromium, zinc and cadmium.
The useful conducting metals all have a greater corrosion
resistance or resistance to aerial oxidation than does iron. The
terms "corrosion resistance" or "resistance to aerial oxidation"
all have reference to the ability of a metal to withstand
oxidative-type corrosion which impairs electrical conductivity. In
general, the type of corrosion which should be avoided is
continuous aerial oxidation or rapid aerial oxidation which
substantially reduces the electrical conductivity of a metal. In
particular, these terms have reference to corrosion induced by
exposure to air, carbon dioxide, water, ozone, etc, and do not have
particular reference to the chemical attack of solutions of strong
acids or bases, etc. Coatings of this type are further described in
H. A. Miller U. S. application Ser. No. 799,967, filed Feb. 17,
1969 and now abandoned, co-filed herewith and entitled Highly
Conductive Carrier Particles. The metal coated carrier particles of
this invention generally have a resistance of less than 10 ohms
with preferred materials having a resistance of less than 1
ohm.
Conductive carriers as described above are excellent for use in
magnetic-brush development wherein it is desired to obtain a
development electrode effect thus producing solid area development.
However, if solid area development is not desired, then it is
necessary to suppress this development electrode effect. The
simplest way to accomplish this result is through the use of highly
insulating carrier particles. When insulating carrier particles are
used, the development electrode effect is suppressed and fringing
development occurs.
In accordance with this invention, high resistance iron carrier
particles can be provided by acid washing and rinsing, as referred
to above, followed by treatment to provide a uniform, adherent iron
oxide surface of high resistivity on the individual particles.
However, in accordance with this embodiment of the invention,
subsequent washings to remove residual acid and waste products are
conducted without the addition of any antioxidant material. After
water washing, the iron is drained to remove surplus moisture and
then dried without subsequent solvent treatment. The drying is
conducted at elevated temperatures so as to induce formation of
surface oxides. Good results are obtained with drying temperatures
of from about 40.degree. C to about 80.degree.C. During the drying
operation, the damp powder is mixed gently in order to keep the
temperature and water content relatively uniform throughout the
mass of powder. During drying, the color of the iron gradually
changes from gray to brown. After drying, the treated powder
exhibits a very high level of surface resistivity. The optimum
drying conditions (i.e., temperature, agitation, humidity, etc,)
needed to produce the desired thin, uniform oxide coatings will be
dependent upon the particular iron powder used as a starting
material. Simple experimentation will readily show which conditions
are optimum for a particular powder chosen. In general, good
results are obtained with air drying temperatures in the range of
from about 40 to about 80.degree.C with a preferred temperature
being in the range of from about 45.degree.C to about 60.degree.C.
The relative humidity of the drying air can vary widely with good
results being obtained at values of 40 percent R.H. and above.
Preferably, the drying air has a relative humidity of 60 percent
and above. Oxide-coated particles can be prepared in this manner
having electrical resistance ranging up to greater than about
10.sup.9 ohms.
When high resistance carrier particles of the above type are mixed
with an appropriate toner material, the resultant developer
composition is found to greatly reduce the development electrode
effect of a magnetic brush. In addition, such a developer
composition induces fringing development with the accompanying
increase in exposure latitude. The iron oxide coating on these
carriers can also be overcoated with a thin plastic film to further
increase the resistance of the carrier and thereby inducing greater
fringe development. In particular, the particles can be overcoated
with continuous, uniform layers of film-forming electrically
insulating resinous material. The polymers or resinous materials
useful in overcoating the carrier particles of this invention can
be selected from a variety of substances. Useful resins must be
film-forming and, in general, they are electrically insulating such
that when coated in desired amounts they will impart the requisite
degree of electrical resistance to the carrier particles. Useful
resins include those capable of being cured, hardened, or otherwise
insolubilized such that when a subsequent resin layer is applied
there is no substantial permeation of a resin layer into an
adjacent layer. Suitable resins include thermosetting resins which
harden upon the application of heat as well as light sensitive
resins which harden upon exposure to actinic radiation. Also
combinations of resins having diverse inherent solubility
characteristics can be used. The different types of useful resins
can be used alone or in various combinations.
Useful light sensitive or light-hardening resins would include
polymeric derivatives of cinnamic acid such as polyvinyl cinnamate,
cinnamoylated polystyrene, ethylene vinyl cinnamate copolymer,
cellulose cinnamate, N-(cinnamoylphenyl)-methane derivatives of
hydroxylated polymers (e.g., partially hydrolyzed polyvinyl
acetate, cellulose acetate, etc.), epoxy resins esterified with
cinnamoyl chloride and the like. Polyvinyl cinnamate succinate and
polyvinyl cinnamate phthalate would be particularly easy to use in
that they can be coated from an aqueous solution. In addition,
photocrosslinkable compositions comprising an unsensitive resin and
a light sensitive crosslinking agent are useful. Such compositions
could comprise an alcohol soluble nylon-type polyamide with, for
example, benzophenone as an initiator, etc.
Useful thermosetting or heat-hardening resins include a wide
variety of materials with formaldehyde condensation products being
exemplary of readily available materials. Particularly useful
materials are formaldehyde condensation products formed with urea,
melamine or with various phenols such as xylenol, cresol,
trimethylphenol, phenol, soligenin, etc. Other resins can also be
used such as thermosetting epoxy resins, polyester-styrene resins
and the like.
Other useful resins would include cellulose resins, such as
cellulose nitrate, cellulose acetate butyrate, etc. and lower alkyl
methacrylate polymers having from one to four carbon atoms in the
alkyl moiety, etc. In general, film-forming polyesters,
polyolefins, polyamides, polycarbonates, etc. can all be used
provided they are applied from suitable liquid vehicles which will
not soften any previously applied layer. Methods for applying
multiple layers of such resins are disclosed in co-pending Miller
U. S. application, Ser. No. 799,968, filed 2-17-69 and now
abandoned, co-filed herewith, and entitled High Resistance Carrier
Particles. Of course, single layers of useful polymeric materials
are also useful. Resin overcoated particles prepared in this manner
generally have an electrical resistance of greater than about
10.sup.12 ohms.
Electroscopic developer compositions can be prepared by mixing from
about 90 to about 99 percent by weight of the present acid-washed
magnetically responsive carrier particles with from about 10 to
about 1 percent by weight of a suitable electroscopic toner
material. The toner used with the carrier particles of this
invention can be selected from a wide variety of materials to give
desired physical properties to the developed image and the proper
triboelectric relationship to match the carrier particles used.
Generally, any of the toner powders known in the art are suitable
for mixing with the carrier particles of this invention to form a
developer composition. When the toner powder selected is utilized
with ferromagnetic carrier particles in a magnetic-brush
development arrangement, the toner clings to the carrier by
triboelectric attraction. The carrier particles acquire a charge of
one polarity and the toner acquires a charge of the opposite
polarity. Thus, if the carrier is mixed with a resin toner which is
higher in the triboelectric series, the toner normally acquires a
positive charge and the carrier a negative charge.
Toner powders suitable for use in this invention are typically
prepared by finely grinding a resinous material and mixing with a
coloring material such as a pigment or a dye. The mixture is then
ball milled for several hours and heated so that the resin flows
and encases the colorant. The mass is cooled, broken into small
chunks and finely ground again. After this procedure the toner
powder particles usually range in size from about 0.5 to about 25
microns, with an average size of about 2 to about 15 microns.
The resin material used in preparing the toner can be selected from
a wide variety of materials, including natural resins, modified
natural resins and synthetic resins. Exemplary of useful natural
resins are balsam resins, colophony and shellac. Exemplary of
suitable modified natural resins are colophony-modified phenol
resins and other resins listed below with a large proportion of
colophony. Suitable synthetic resins are all synthetic resins known
to be useful for toner purposes, for example polymers, such as
vinyl polymers including polyvinyl chloride, polyvinylidene
chloride, polyvinyl acetate, polyvinyl acetals, polyvinyl ether and
polyvinyl polyacrylic and polymethacrylic esters; polystyrene and
substituted polystyrenes or polycondensates, e.g., polyesters, such
as phthalate resin, terephthalic and isophthalic polyesters,
maleinate resin and colophony-mixed esters of higher alcohols;
phenol-formaldehyde resins, including colophony-modified phenol
formaldehyde condensates, aldehyde resins, ketone resins,
polyamides and polyadducts, e.g., polyurethanes. Moreover,
polyolefins, such as various polyethylenes, polypropylenes,
polyisobutylenes and chlorinated rubber are suitable. Additional
toner materials which are useful are disclosed in the following U.
S. Pat. Nos. 2,917,460; RE 25,136; 2,788,288; 2,638,416; 2,618,552
and 2,659,670.
The coloring material additives useful in suitable toners are
preferably dyestuffs and colored pigments. These materials serve to
color the toner and thus render it more visible. In addition, they
sometimes affect, in known manner, the polarity of the toner. In
principle, virtually all of the compounds mentioned in the Color
Index, Vol. I and II, Second Edition, 1956, can be used as
colorants. Included among the vast number of suitable colorants
would be such materials as Nigrosin Spirit soluble (C.I. 50415),
Hansa Yellow G (C.I. 11680), Chromogen Black ETOO (C.I. 14645),
Rhodamine B (C.I. 45170), Solvent Black 3 (C.I. 26150), Fuchsine N
(C.I. 42510), C.I. Basic Blue 9 (C.I. 52015), etc.
The following examples are included for a further understanding of
the invention and all indications of mesh sizes have reference to
the U.S. Standard Sieve Series.
EXAMPLE 1
A 2,500 g. quantity of a commercial iron powder (Glidden Iron 388,
Glidden-Durkee Div. SCM Corp.) is poured into 1,500 ml. of 2N
sulfuric acid solution over a 10-second period. The iron powder
used has a particle size such that it will pass through a 140 mesh
screen and be retained by a 170 mesh screen. The resistance of the
iron carrier as measured in the standard resistance test referred
to above is 2,400 ohms. After addition of the iron to the sulfuric
acid, stirring is continued for 60 seconds whereupon the reaction
mixture is diluted to 4,000 ml. with cold tap water. The mixture is
allowed to settle for 10 seconds and then the brown, supernatant
liquid is decanted along with a considerable quantity of black
greasy scum on the surface. Decantation rinsing is repeated 8 more
times with 2,000 ml. volumes of water. The slurry is agitated after
each addition of rinse water so as to briefly suspend all iron
powder. After suspension, the powder is allowed to settle and the
supernatant liquid is again decanted along with suspended dirt and
other unwanted materials. After the final water rinse, the iron is
drained and rinsed 4 times with 600 ml. volumes of anhydrous
methanol with thorough mixing after each addition followed by a
settling period of 10 seconds prior to decantation. Following the
final alcohol rinse, the drained iron is suction filtered on a
Buchner funnel and the resulting damp powder is dried in a thin
layer (1/16 inch or less) on a glass sheet. The powder is mixed
continuously during drying with heat being provided by infrared
radiation from two 250 watt infrared bulbs at a distance of about
45 cm. from the powder. The two infrared bulbs provide sufficient
heat to prevent the powder from being cooled excessively by
evaporation of the residual methanol. The ambient air is at a
temperature of about 21.degree. C and a relative humidity of
slightly less than about 40 percent. Upon drying, the resistance of
the powder was measured in the standard test referred to above and
found to be 16 ohms. The dry powder weighs 2,468 grams which
represents a total loss of about 1.3 percent in dirt, surface
oxide, pyrites, etc, as well as extremely finely divided iron
powder decanted in washing. A magnet placed in all of the dirt,
etc, removed from the starting iron attracted only a minute amount
of material indicating that only very little of the material lost
is actually iron. Next, two magnetic brush developer compositions
are prepared from the acid-washed iron and with an equal quantity
of untreated starting material. The two carriers are each mixed
with 3 percent by weight of a black, styrene co-polymer toner,
having a particle size of from 1-5 microns. The toner material
charges positively on the carrier particles. The two developer
mixtures are tested in a magnetic-brush development apparatus. The
apparatus for testing comprises a cylindrical aluminum tube
arranged to rotate axially in a horizontal position about a fixed
permanent magnet. The permanent magnet has its poles oriented such
that when the magnetic particles are present, a magnetic brush is
formed on top of the cylinder. In the test procedure, this
apparatus is run for 15 minutes with the magnetic brush in contact
with an electrophotographic element comprised of a conductive
support coated with a photoconductive layer of an organic
photoconductor in a resin binder. The developer formed using the
untreated carrier particles shows considerable tendency to leave a
scum or deposit on the photoconductor after repeated use; whereas,
the developer containing acid-treated carrier shows very little
tendency to leave a scum. In addition, when the two carrier
particles are tested in the same apparatus using no toner, the
acid-treated carrier particle produces no visible deposit during
the test; while the untreated carrier deposits a black layer having
a density of about 0.8. The two developer mixtures are then used to
develop an electrostatic latent image carried on a photoconductive
element as described above. The developer containing the
acid-treated carrier gives better overall image quality with more
solid area development while showing less sensitivity to variations
in the electrical potential applied to the magnetic brush.
EXAMPLE 2
A quantity of 454 g. of high density electrolytic iron powder
(Glidden 475, Glidden-Durkee Div. SCM Corp.) is poured rapidly with
stirring into 250 ml. of a 5 percent hydrochloric acid solution in
a 1 liter beaker. The iron powder has a particle size such that it
will pass through a 60 mesh screen and be retained by a 120 mesh
screen. In addition, the resistance of this iron powder as measured
in the standard resistance test described above is 640,000 ohms.
The slurry of iron powder and hydrochloric acid is mixed
continuously for 2 minutes at which time the reaction of the acid
on the iron powder subsides. The acid-treated iron is then rinsed
four times by decantation with 750 cc. of a 0.5 percent solution of
sodium nitrite in distilled water. After the last water rinse, the
iron is drained and rinsed twice with anhydrous ethanol. Excess
alcohol is then removed by filtration using a Buchner funnel for 10
minutes. The damp powder is rapidly dried by sprinkling it
repeatedly through a current of dry air at a temperature of
approximately 30.degree.C and a relative humidity of less than 30
percent. The powder is fully dried within about 4 minutes. The
yield is 450 grams. After drying, the acid-treated powder is
measured for resistance in the standard resistance test and found
to be 0.2 ohms. Next, the acid-treated carrier particles are placed
in the mechanical magnetic-brush apparatus as described in Example
1. The apparatus is run using the treated carrier particles for a
period of 15 minutes. At the end of this period no visible scum is
deposited on the electrophotographic element used. An equivalent
quantity of uncoated control carrier material when used in the test
apparatus for 15 minutes produces a deposit on the photoconductive
element which measures 0.25 in density using a standard
densitometer. Next, the acid-treated carrier and the control
carrier are mixed with 5 percent portions of a blue toner powder
and again subjected to the standard scumming test. The developer
prepared with the acid-washed carrier particles produced a slight
amount of scum which is barely visible; whereas, the control
developer produces a large amount of scum which is readily visible.
In addition, the control developer when in use is subject to a
large degree of toner throw-off while the developer of the present
invention exhibits considerably less toner throw-off. The two
developer compositions are then used to develop an electrostatic
latent image carried on an electrophotographic element. The
developer containing the acid-washed carrier gives good image
quality with excellent solid area development both with and without
bias on the magnetic brush. The control developer gives some image
development; however, the solid areas are developed in a very
uneven manner. The hue of the two developed images shows the image
formed from the control developer to be less saturated than the
image formed from the developer containing the acid-washed carrier.
The developer containing the acid-treated carrier is then placed in
an open 1 liter beaker and held for 3 weeks under average room
conditions (about 20.degree.C and 45 percent relative humidity). At
the end of this period, the developer is measured for resistance
and found to be substantially unchanged from the resistance value
at the start of the test period. In addition, when this developer
is tested again for image development, the results obtained are
substantially the same as those obtained when using a freshly
prepared developer composition in accordance with this example.
EXAMPLE 3
A 5 kilogram quantity of spherical iron particles, of a size such
that will pass through a 150 mesh screen and be retained by a 200
mesh screen, is poured into 3 liters of a 1:15 dilution of
concentrated nitric acid at 20.degree.C. The mixture is slurried
for 2 minutes and then diluted to 10 liters with tap water at about
5.degree.C. The diluted mixture is allowed to settle for about 10
seconds and the supernatant liquid and suspended contaminants are
decanted. The initially black iron powder appears silver-gray in
color after this acid treatment. The acid-treated iron is then
subjected to 5 decantation rinses using tap water at 20.degree.C.
whereupon the surplus water is drained from the iron powder by
suction in a Buchner funnel. The damp iron powder is spread out to
a thickness of about 1 inch in a plastic tray and allowed to dry.
Four 250 watt infrared bulbs are positioned approximately 50 cm.
from the tray to warm the powder during drying. During the drying
operation, the iron is turned over continuously while maintaining
an average depth of about 21/2 cm. As the powder dries, it turns
progressively more brown in color. The weight of the dry product is
4,986 grams. After drying, the resistance of the material is
measured and found to be 2 .times. 10.sup.9 ohms as compared to 2.8
.times. 10.sup.6 ohms for the starting material. A hand-held bar
magnet is then used to attract the treated carrier material. The
amount of carrier material which is picked up by the bar magnet is
measured and the magnet is cleaned and repeated again using the
starting iron particles. It is found that the bar magnet will
attract 5 percent by weight more of the treated carrier material
than the untreated material. Next, two developer compositions are
prepared using the treated carrier and the control carrier. Each
developer contains 4 percent by weight of a black toner powder
having an average particle size of 2 microns and comprising a
nigrosine colorant in a styrene polymeric binder. The two developer
compositions are then used in the mechanical brush apparatus
described in Example 1. The acid-treated carrier containing
developer produces images of good quality with excellent fringe
development being obtained. In addition, a wide exposure latitude
is obtained with the developer containing acid-treated carrier. The
control developer gives only acid-treated carrier. The control
developer gives only very limited exposure latitude and only slight
fringing development.
EXAMPLE 4
A 200 g. quantity of iron powder in the form of flat iron leaflets
having a particle size such that they will pass through a 60 mesh
and be retained by an 80 mesh screen is placed into the bottom of a
glass tube having an inside diameter of about 3 cm. and about 60
cm. long. One liter of 10 percent trichloroacetic acid solution is
pumped upward through the iron in he tube. The solution is
circulated the the iron powder 4 times in 51/2 minutes. Suspended
dirt and other contaminants are trapped in a wool-felt filter
before recirculation of the solution. The acid is then replaced
with cold tap water which is forced upward through the bed of iron
powder at a rate sufficient to remove unwanted small particles of
contaminants without carrying away any appreciable amount of the
screened carrier material. The water flow rate is approximately 1
liter per 100 seconds. After 15 minutes of washing, the wet
material is transferred to a suction funnel to remove surplus
moisture. The top of the funnel is provided with a plastic cap to
exclude air and nitrogen is pumped into the cap at a rate
sufficient to prevent collapse of the cap. After 30 minutes, the
nearly dried powder is removed and finally dried rapidly by
sprinkling it repeatedly through a current of dry air at about
20.degree.C and a relative humidity of about 40 percent. The
resistance of the final product as measured in the standard test as
described above is 37 ohms compared to 1,200 ohms for the starting
material. Equal quantities of the starting material and the
acid-treated material are used to prepare developer compositions,
each containing 3 percent by weight of the black toner of Example
1. When used to develop electrostatic latent images, both
developers give solid area development in a standard magnetic brush
apparatus; however, the developer with the acid-treated highly
conductive carrier produces substantially better solid area fill-in
and is less sensitive to changes in the electrical bias of the
magnetic brush than is the control developer.
EXAMPLE 5
A 1,600 g. quantity of commercial iron powder in the form of
flattened grains (Glidden Iron 412, Glidden-Durkee Div. SCM Corp.)
is acid-treated as follows. The starting iron powder has a nominal
particle size such that it will pass through a 60 mesh screen and
be retained by a 120 mesh screen; however, the powder has an
extremely large portion (about 15 percent) of much more finely
divided material. The starting material is placed on a 120 mesh
plastic screen and sprayed with an acid solution comprising 200 cc.
of concentrated sulfuric acid and 3 liters of tap water at about
15.degree.C. The iron is spread out evenly over an area of about
700 sq. cm. and sprayed uniformly with the acid at a rate of about
25 ml. per second under about 10 pounds pressure through a plastic
spray nozzle. The force of the spray jet helps to separate small
contaminants and force them down through the plastic screen. Next,
the powder is rinsed with a 0.2 percent solution of hydrazine
sulfate. After about 10 liters of the rinse solution has been
sprayed over the iron, the material is drained, rinsed free of
surplus water by spraying with 2 liters of isopropanol and dried in
a current of dry air at a temperature of about 32.degree.C and a
relative humidity of about 35 percent. The velocity of the air is
maintained at a sufficient rate to produce continuous movement of
the powder during drying. In addition, further agitation is
provided by brushing the iron during the drying step with a small
brush. After the iron is completely dry, the air is turned off, but
manual brushing action is continued for 3 minutes to assist in
sifting out any particles having a size smaller than 120 mesh. The
resistance of the treated material is measured and found to be 7
ohms as compared to 900 ohms for the starting material. Next, the
carrier material is mixed with 3 percent by weight of a yellow,
styrene base toner which charges negatively with respect to the
iron carrier particles. The resulting developer composition is used
to develop positively charged electrostatic latent images carried
on an electrophotographic element. Excellent solid area development
is obtained and the resultant image is of a high quality and has a
brilliant yellow hue. A control developer prepared with the same
yellow toner and the starting iron carrier, which has been screened
to reduce the number of fine particles, gives images of poor
quality having substantially less solid fill-in and considerably
less hue saturation. This loss of color brightness appears to be
caused by loose dirt and oxide on the surface of the control
carrier material, which dirt mixes with toner and is transferred to
the electrostatic image. The control developer is also undesirable
in that it is much more sensitive to changes in bias potential on
the magnetic brush.
EXAMPLE 6
Two kilograms of iron treated as in Example 1 above are coated with
a thin continuous layer of nickel by electroless plating for 30
minutes at about 95.degree.C in a bath of the following
composition:
Nickel(ous)chloride N.sup.. Cl.sub.2.sup.. 6H.sub.2 O 67.5 g.
Sodium citrate Na.sub.3 C.sub.6 H.sub.5 O.sub.7.sup.. 2H.sub.2 O
123.0 g. Ammonium chloride NH.sub.4 Cl 75.0 g. 28% Ammonia solution
150.0 ml. Sodium Hypophosphite NaH.sub.2 PO.sub.2.sup.. H.sub.2 O
16.5 g. Water to make 1500.0 ml.
The nickel-plated powder is removed from the bath and washed with
six changes of cold water, rinsed three times with ethanol, suction
filtered and dried at room temperature. The resistance of the dry
powder is measured in the standard resistance test and found to be
less than 1/2 ohm. The nickel-coated carrier is then used to
prepare a developer composition as in Example 1. Electrostatic
latent images developed with this developer show excellent solid
area fill-in.
EXAMPLE 7
A 700 g. quantity of a stainless steel iron powder having a
particle size such that it will pass through a 200 mesh screen and
be retained by a 325 mesh screen is treated with acid in the same
manner as in Example 1 using 500 ml. of a 1:19 aqueous solution of
sulfuric acid followed by 12 decantation rinses with 1,500 ml.
quantities of water at 38.degree.C. After the last water rinse, the
residual water is drained out by placing the iron in a suspended
cotton sack for 15 minutes. The iron is then placed in a shallow
glass tray and dried with a current of air at room temperature
while keeping the level of the iron at about 11/4 cm. depth and
turning over the iron every 2 or 3 minutes with a hand spatula.
During the course of drying, the iron acquires a gray color. The
final product is measured in the standard resistance test and found
to have a resistance of 10 megohms as compared to 22,000 ohms for
the starting material. The result carrier is used to prepare a
developer composition and used to develop an electrostatic latent
image as in Example 1. Good fringing development is obtained using
this developer. A similar developer composition prepared using the
control carrier and the toner of Example 1 gives neither good solid
area nor good fringing development.
EXAMPLE 8
A one kilogram quantity of iron powder as prepared in Example 3 is
mixed with 300 ml. of a 7 percent solution of polyvinylcinnamate
light sensitive resin in methyl collosolve acetate. The powder is
spread out on a glass surface and dried at room temperature. The
dried powder is then exposed to a 35 ampere arc lamp for 10 minutes
while continuously stirred to insure uniform exposure. This
procedure is repeated four times resulting in four distinct resin
coatings on each particle. The particles are then measured in the
standard resistance test and found to have a resistance value of
greater than about 10.sup.15 ohms. A developer composition is
prepared with this carrier and used to develop an electrostatic
latent image as in Example 1. Excellent fringe developed images are
obtained over a wide range of exposures.
The invention has been described in detail with particular
reference to certain preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *