U.S. patent number 3,898,171 [Application Number 05/421,456] was granted by the patent office on 1975-08-05 for electroscopic powder with sharp melting point containing sucrose benzoate and a thermoplastic resin.
This patent grant is currently assigned to Addressograph-Multigraph Corporation. Invention is credited to Virgil W. Westdale.
United States Patent |
3,898,171 |
Westdale |
August 5, 1975 |
Electroscopic powder with sharp melting point containing sucrose
benzoate and a thermoplastic resin
Abstract
An electroscopic powder having a sharp melting point which is
particularly adaptable for use in high speed electrostatic copying
machines is formulated with sucrose benzoate in the range of 40 to
80% by weight and a thermoplastic resin such as a polyamide,
polyacrylate or polyurethane in the range of 10 to 40% by weight
and optionally a metal soap in the range of 0.01 to 3.0% by weight
with the remainder consisting of coloring agents such as pigments
or dyes.
Inventors: |
Westdale; Virgil W. (Chagrin
Falls, OH) |
Assignee: |
Addressograph-Multigraph
Corporation (Cleveland, OH)
|
Family
ID: |
23670597 |
Appl.
No.: |
05/421,456 |
Filed: |
December 3, 1973 |
Current U.S.
Class: |
430/108.4;
430/108.3; 430/109.3; 430/109.5 |
Current CPC
Class: |
G03G
9/09733 (20130101); G03G 9/09791 (20130101) |
Current International
Class: |
G03G
9/097 (20060101); G03g 009/00 () |
Field of
Search: |
;252/62.1P ;96/1SD |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Nelson; P. A.
Attorney, Agent or Firm: Kondzella; Michael A.
Claims
I claim:
1. An electroscopic powder for developing electrostatic images
having a sharp melting point range comprising a blend of sucrose
benzoate in the range of from 40 to 80% and a thermoplastic resin
selected from the group consisting of polyamides, polyacrylates and
polyurethanes in the range of from 10 to 40% by weight.
2. An electroscopic powder according to claim 1 which includes a
metal soap selected from the group consisting of lithium, calcium,
barium, zinc and aluminum salts of C.sub.12 to C.sub.18 carboxylic
acids present in an amount in the range of from 0.01 to 3.0% by
weight.
3. An electroscopic powder according to claim 1 which has a melting
point in the range of 75.degree. to 150.degree.C.
4. An electroscopic powder according to claim 1 which melts
completely within a 5.degree. melting range.
5. An electroscopic powder according to claim 1 which melts
completely within the range of from 105.degree. to 110.degree.C.
Description
BACKGROUND OF THE INVENTION
This invention relates to electroscopic powders which are useful
for developing latent electrostatic images produced by
electrophotographic copying techniques. More particularly, it
relates to electroscopic powders which have been formulated from
materials which serve to improve the fixability of the powder onto
the copy sheet.
Photoelectrostatic copying processes in which a photoconductive
medium is imaged to produce a differential electrostatic charge
which is then developed with an electroscopic powder or toner are
well known. A wide variety of photoconductive media may be employed
such as elemental photoconductors, photoconductive crystalline
metal compounds and organic photoconductors, both monomeric and
polymeric.
Techniques are well known for developing the differentially charged
photoconductive medium including magnetic brush development, powder
cloud development, liquid development and cascade development.
The formulation of electroscopic powders for use in a particular
electrophotographic copying environment has been widely explored.
The powders are applied by the various techniques mentioned above
and ultimately fixed so that they will adhere to the copy material
being used. The copy material may be the photoconductor itself such
as in the case of zinc oxide coated paper. In other systems the
powder image is first produced on a photoconductive drum and then
transferred to a sheet of plain paper where the powder image is
fixed. In either case the electroscopic powder must be permanently
fixed to the material which is to become the permanent copy.
In the copying systems previously known the techniques of fixing
the image onto the copy generally depended upon the use of heat in
order to fuse a thermoplastic resin powder contained in the
electroscopic powder onto the copy material. The use of heat energy
is generally acceptable but prolonged heating at high temperatures
causes some problems. For example, the hazard of igniting papers or
at least charring them in the circumstance that there is a paper
jam in the paper delivery system is an ever present danger. In
addition the introduction of excessive amounts of heat into the
working environment causes some discomfort.
Pressure fusing obviates some of the disadvantages inherent in
lengthy heat fusing cycles, but pressure fusing requires specially
formulated toners.
One important consideration is the time which is required to impart
sufficient heat to the thermoplastic powder so that it will
properly soften and coalesce. The rate of output of reproductions
in any electrophotographic copying system is only as fast as the
slowest processing step which heretofore was the heat fusing
operation.
Electrostatic powders or toners have been suggested which are
formulated especially for rapid fusing. It has been found, however,
that because of their broad range of melting points they tend to
produce reproductions whose images are feathered and generally of
poor resolution when heat fused because of the presence of very low
melting point constituents which when combined together with higher
melting point materials cause the images to spread out.
OBJECTS OF THE INVENTION
It is accordingly a general object of this invention to provide an
improved electroscopic powder having utility in high speed
electrophotographic copying machines.
It is another object of the instant invention to provide an
improved electroscopic powder for use in high output
electrophotographic copying machines capable of producing high
quality images.
It is another object of this invention to provide a rapid fusing
electroscopic powder having a sharp melting point.
Other objects and advantages of this invention will become apparent
from the following detailed disclosure and description.
SUMMARY OF THE INVENTION
It has been found that the use of sucrose benzoate in a major
proportion results in electroscopic powder formulations which have
a sharp melting point, are rapidly fusible and produce sharp images
upon development. Toners formulated using sucrose benzoate have
been found to adhere well to the copy sheet. They have low fusing
temperatures and yet do not soften or melt so as to cause
agglomeration during storage of toner. Greater copying speeds are
therefore attainable using these toners.
Another advantage of using the toners of this invention is that
copies prepared using these toners do not display high background
when printing in very low humidity atmospheres as is the case with
other toners. Developer mixes utilizing these toners can, for
example, be allowed to stand in a dry atmosphere, that is, one in
which the relative humidity is as low as about 10%, for a number of
days without affecting the triboelectric properties of the
toner.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Electroscopic powders of the instant invention comprise sucrose
benzoate in the range of 40 to 80% by weight, a resin component
which may be a polyamide resin, a polyacrylate resin, a
polyurethane resin or other thermoplastic resin having similar
properties in the range of 10 to 40%, a coloring agent in the range
of 1 to 10% and various other optional ingredients as hereinafter
described.
Sucrose benzoate, C.sub.12 H.sub.14 O.sub.3 (C.sub.6 H.sub.5
--COO).sub.7 is a non-crystalline, non-polymeric frangible solid
having a softening point of around 98.degree.C. When used with a
suitable thermoplastic resin and coloring agent in a concentration
of about 40 to 80% by weight a toner having a sharp melting range
which is particularly adaptable to rapid electrophotographic
copying results. Such toners also have a relatively high point of
tackification, that is, they will stay in their physical state
without significantly changing as their melting point is
approached. At that point their physical state changes abruptly so
that powder images produced using these toners can be fused at
higher speeds for a given amount of energy input than toners
previously available.
Coloring agents useful in this invention include carbon black,
Nubian Resin Black and other pigments or dyes.
Suitable thermoplastic resins include polyamide resins produced by
reaction of dicarboxylic acids or their esters with polyamino
compounds such as diamines. Preferred esters are the methyl, ethyl,
and propyl esters. Suitable polyamino compounds include
ethylenediamine, tetramethylenediamine, pentamethylenediamine,
piperazine and diethylenetriamine. One group of particularly
suitable polyamides sold under the trademark "VERSAMID" by General
Mills Company are prepared from dimer acids and polyamines, for
example the condensation product of 9,11-linoleic acid and
9,12-linoleic acid with ethylene diamine. Other suitable polyamide
resins are available from the Krumbhaar Resin Division of Lawter
Chemicals, Inc. under the trademark "POLYMID."
Another group of thermoplastic resins which can be used in the
toners of this invention are the acrylic resins or polyacrylates.
Examples of suitable polyacrylates include polymethylmethacrylate
and polyethylmethacrylate sold under the trademark "ACRYLOID" by
Rohm and Haas Company. Acrylic copolymers can also be used, such as
the copolymers of vinyl monomers and alkyl acrylates, for example,
those sold under the trademark "IONAC" by Ionac Chemical Company.
One such copolymer is a copolymer of styrene and butylmethacrylate
which is sold under the trademark "IONAC RP 60."
An optional ingredient in the toners of this invention is a metal
soap, for example, a lithium, calcium, barium, zinc or aluminum
salt of a C.sub.12 to C.sub.18 carboxylic acid such as lauric acid
or stearic acid. Such soap is desirable where the toner and the
developer mix incorporating the toner are exposed to the excessive
stresses present in high speed machines. It has been found that the
presence of these metal soaps in a concentration of from 0.01 to
3.0% by weight prolongs the life of the developer mix where it is
tumbled and compacted rapidly such as when producing 50 to 60
copies per minute or more. The metal soaps have also been found to
prolong the life of the mix where the equipment is used for long
periods at high speeds. It is not necessary to include the metal
soaps where the machine is operated at slower copymaking speeds or
at high speeds only intermittently.
In preparing the electroscopic powders of this invention the
resinous materials are first reduced to their molten state and the
sucrose benzoate, various coloring agents and the metal soap, if it
is to be added, are then mixed into the molten resin.
The following examples are given to illustrate the preferred
embodiments of this invention. It will be understood that these
examples are merely for the purpose of illustration and are not
intended as limitations upon the scope of the invention, which is
defined in the claims appended hereto.
In all the examples, the amounts shown are percent by weight of the
electroscopic powder formulations.
EXAMPLE I
Ingredient Per Cent ______________________________________ Sucrose
benzoate 55.3 Styrene-butylmethacrylate copolymer IONAC RP 60 Ionac
Chemical Company 32.5 Zinc laurate 2.1 Carbon black 4PCO5
Richardson Ink Co. 2.8 Nubian Resin Black 7.3
______________________________________
The sucrose benzoate and styrene-butylmethacrylate copolymer were
added to a 1/2 gallon can, melted and agitated well. Zinc laurate
was added and agitated at 3,000 rpm. for 8 minutes at a temperature
of 171.degree.C. The carbon black was added in the form of a 50%
dispersion of carbon black in VERSAMID 930 polyamide resin, and
agitated for 15 minutes at 4,500 rpm. at 182.degree.C. The Nubian
Resin Black was added and the mixture agitated for 15 minutes at
4,800 rpm. at a temperature of 182.degree.C maximum. The molten
mass was removed and immediately poured into shallow pans so as to
form a large thin wafer which was rapidly cooled by forced air in
order to prevent individual constituents from separating out of the
mixture or otherwise stratifying. The large wafer formation was jet
milled at 10 lb. per hour and 100 psi. to an average particle size
ranging from under 1 micron to about 50 microns in size.
The powder was classified according to particles which pass through
a 100 mesh screen so that the largest particle size was under 149
microns.
A developer mix using 40 parts of RZ 150 iron particles to 1 part
of the toner prepared according to the foregoing description was
placed in a 1-gallon can and rolled on a roll mill for one-half
hour.
The resulting developer mix was used in a commercial
electrophotographic copying machine, the AM 5000 manufactured by
Addressograph-Multigraph Corporation, which utilizes pressure
fixing. The copies prepared on zinc oxide coated paper using this
developer were sharp and dark.
EXAMPLE II
Ingredient Per Cent ______________________________________ Sucrose
benzoate 78.4 Polyurethane resin P250-2 Hooker Chemical Co. 10.1
Zinc laurate 2.1 Carbon black ELF-5 Cabot Carbon Co. 3.8 Nubian
Resin Black 5.6 ______________________________________
The sucrose benzoate was carefully melted to prevent burning since
it was necessary to provide a high temperature in order to melt the
polyurethane. The other ingredients were added in order, first
dissolving the polyurethane with the carbon black and Nubian Resin
Black being dispersed at 4,500 rpm. The toner was then prepared in
the same manner as in Example I.
A developer mix was prepared using 35 parts of the toner to 1,225
parts of RZ 150 iron particles.
The resulting developer was used to make satisfactory copies in a
commercial electrophotographic copying machine, the AM 2000
manufactured by Addressograph-Multigraph Corporation which was
equipped with a continuous oven fuser and a magnetic brush
developer. Zinc oxide coated paper was utilized for making
copies.
EXAMPLE III
Ingredient Per Cent ______________________________________ Sucrose
benzoate 69.0 Acrylic resin Acryloid B 82 Rohm and Haas Co. 20.7
Zinc laurate 2.1 Carbon black ELF-5 Cabot Carbon Co. 1.4 Nubian
Resin Black American Cyanamid Co. 6.8
______________________________________
The sucrose benzoate and acrylic resin were placed into a
half-gallon can, melted and agitated at 2,000 rpm. The zinc laurate
was added, melted and agitated at 3,000 rpm.
The carbon black was then added, dispersed in the mixture resulting
from the previous additions and agitated at 4,500 rpm. The Nubian
Resin Black was then added, dispersed and agitated at 4,500 rpm.
until it was completely dispersed. The temperature held at
177.degree.C. and reached a maximum of 179.degree.C.
The resulting mixture as jet-milled at 15 lb. per hour feed at a
pressure of 90 psi. resulting in a satisfactory particle size
distribution which peaked at 8.1 microns on the volume differential
curve for this formulation.
At a feed of 10.4 lb. per hour the toner was a finer particle size
and volume differential curve was broader.
Jet-milling at 18.8 lb. per hour feed at 85 psi. resulted in a more
desirable particle size distribution.
Seventy-four grams of this toner formulation were mixed with 2,950
grams of RZ 150 iron carrier particles placed in a 1-gallon can and
tumbled on a roll mill for one-half hour. Satisfactory copies were
made on the commercial electrophotographic copying machine of
EXAMPLE I.
EXAMPLE IV
Ingredient Per Cent ______________________________________ Sucrose
benzoate 55.2 Acrylic resin Acryloid B 82 Rohm and Hass Co. 34.5
Zinc laurate 2.1 Carbon black ELF-5 Cabot Carbon Co. 1.4 Nubian
Resin Black Z-1630 American Cyanamid Co. 6.8
______________________________________
The ingredients shown above were processed according to the
procedure of Example III except that the mixture was jet-milled at
a feed of 12.1 lb. per hour at 90 psi.
Mixture softened at 105.degree.C. and melted at 110.degree.C.
Copies were made using a ratio of 30 parts iron carrier particles
to 1 part toner.
The electrostatic copier used was equipped with a pressure fixing
device so that the powder could be permanently adhered to the
photoconductive member by passing between a pair of pressure
rollers. The powder readily adhered to the coated paper under a
pressure of 300 lb. per lineal inch, assuming a line contact
between the pressure rollers.
In order to measure the effectiveness of the pressure fixing step
of the powder image, a procedure is used whereby the surface of the
image is mechanically rubbed with a piece of white cloth attached
to a mechanical wiper under controlled conditions of pressure and
rubbing action.
A standard piece of test equipment is utilized to make this rub-off
test measurement and is identified as an AATCC Crock Meter
(American Association of Textile Colorists and Chemists). This
device is equipped with a mechanically operated finger that applies
a constant rubbing action to the surface of a copy sheet bearing a
pressure fixed image. The finger applies a force of 319 grams to
the surface over which it rubs. The rubbing surface of the finger
is 1.5 centimeters in diameter covered with a special white cloth
and the rubbing action is back and forth in a straight line along a
10.2 centimeter distance along the surface of the test
specimen.
In order to determine the permanence of the pressure fixed image,
the image density of the electrostatic copies is adjusted so that
the solid areas measure 1.0 to 1.10 density units on the copies.
The image density measurements are obtained by using a reflective
densitometer. This image density represents a standard value so
that the test results are comparable between different toners,
different copying machines, different paper and varying light
conditions. The surface of the rubbing finger covered with a piece
of the special test cloth is allowed to move across the surface of
the sample through 5 rubbing cycles each rubbing cycle representing
a 20.4 centimeter movement or a total rubbing distance of 102
centimeters.
The test cloth is removed from the finger and the optical density
of the toner picked up on the surface of the cloth as a result of
the rubbing action is read using the same densitometer. The results
are shown in Table 1.
TABLE 1 ______________________________________ Rub-Off Original
Copy Density Front Center Back
______________________________________ 0.80 - 1.0 0.636 0.800 0.765
______________________________________
The Fisher-Johns melting point of the toner was 105.degree. to
110.degree.C.
EXAMPLE V
Ingredient Per Cent ______________________________________ Sucrose
benzoate 54.6 Polyamide resin "POLYMID 1060" Lawter Chemical
Company 32.9 Carbon black 4PCO5 Richardson Ink Co. 2.9 Zinc laurate
2.2 Nubian Resin Black Keystone Aniline and Chemical Co. 7.5
______________________________________
The polyamide resin is melted and the carbon black, zinc laurate,
sucrose benzoate, and Nubian Resin Black added in order and the
entire mixture jet-milled at 10 lb. per hour feed at a pressure of
95 psi. which was found to give a satisfactory particle size
distribution.
A mixture of 85 grams of the resulting toner and 3,400 grams of RZ
200 iron powder (+ 325) was placed in a one-gallon can and rolled
on a roll mill for one-half hour. Toner was then prepared according
to the procedure of EXAMPLE I.
Copies were prepared on the commercial electrostatic copier
described in EXAMPLE I. It was found that copies prepared were
clean with no iron print-out and the density of the copies produced
was maintained throughout a run of over 2,000 copies. Over 8,000
copies were made by retoning.
The toner produced using this formulation has a melting point range
of 101.degree. to 104.degree.C. as determined on the Fisher-Johns
melting point apparatus.
In general in order to prepare a suitable developer mix the
electroscopic powder of this invention is combined with a suitable
carrier as described above. The ratio of toner to carrier in parts
by weight is in the range of 1:15 to 1:60 where the developer mix
is to be used with a magnetic brush system and iron particles are
used as the carrier. Where glass beads or other carrier of the type
used in cascade systems are used the ratio of toner to carrier can
be as low as about 1:80.
The unique feature of the instant invention resides in the
combination of sucrose benzoate with a thermoplastic resin selected
from the group consisting of polyamides, polyacrylates and
polyurethanes, which produces a toner formulation which is fixable
by heat or pressure and is adaptable to use in high speed machines.
Such toners have a melting point within the range of 75.degree. to
150.degree.C. and melt completely within a range of about
5.degree.. An especially preferred toner has a melting range of
105.degree. to 110.degree.C. Because of the sharp melting point
displayed by such toner formulations, they demonstrate surprising
longevity when combined with carrier particles in the environment
of high speed electrostatic copiers, giving acceptable performance
in terms of density of image, clean background of copy, and the
ability to be pressure fixed to the copy sheet by using pressures
in the range of 175 to 350 lb. per lineal inch and preferably 275
to 350 lb. per lineal contact inch as well as the ability to be
fused by heat in a relatively short period of time.
* * * * *