U.S. patent number 3,653,894 [Application Number 04/884,307] was granted by the patent office on 1972-04-04 for electroconductive paper, electrographic recording paper, and method of making same.
This patent grant is currently assigned to Allied Paper Incorporated. Invention is credited to Bert Growald, Robert M. Levy, Robert J. Thiessen.
United States Patent |
3,653,894 |
Levy , et al. |
April 4, 1972 |
ELECTROCONDUCTIVE PAPER, ELECTROGRAPHIC RECORDING PAPER, AND METHOD
OF MAKING SAME
Abstract
Electroconductive paper utilizing montmorillonite clay in a
binder as the conductive agent is disclosed. The electroconductive
paper can be overcoated with a dielectric film or a coating of a
photoconductor in a non-conductive or dielectric binder for an
electrostatic printing purpose. When the montmorillonite clay is in
a non-water-sensitive binder such as a latex binder, an aqueous
coating of photoconductive material can be used.
Inventors: |
Levy; Robert M. (Kalamazoo,
MI), Thiessen; Robert J. (Richland, MI), Growald;
Bert (Los Altos, CA) |
Assignee: |
Allied Paper Incorporated
(Kalamazoo, MI)
|
Family
ID: |
27073938 |
Appl.
No.: |
04/884,307 |
Filed: |
December 11, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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565685 |
Jul 18, 1966 |
|
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565686 |
Jul 18, 1966 |
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Current U.S.
Class: |
430/63; 162/138;
427/391; 430/91; 430/96; 427/121 |
Current CPC
Class: |
G03G
5/101 (20130101) |
Current International
Class: |
G03G
5/10 (20060101); G03g 007/00 (); C08c 017/16 ();
C09d 005/24 () |
Field of
Search: |
;96/1,1PC,1.5,1.7
;117/156,201,218,215,155U ;162/138,181,162 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Lesmes; George F.
Assistant Examiner: Wittenberg; M. B.
Parent Case Text
This application is a continuation-in-part of applications Ser. No.
565,685 and 565,686 both filed on July 18, 1966, and both now being
abandoned. The disclosures of said applications are incorporated
herein by reference.
Claims
Having thus described the invention, what is claimed is:
1. In an electroconductive paper base sheet comprising a cellulosic
web containing a conductive agent and an insulating binder for said
conductive agent, said binder comprising a film-forming
thermoplastic or thermosetting resinous binder, the improvement
wherein said conductive agent comprises montmorillonite clay in a
proportion sufficient for imparting a resistivity of about 10.sup.9
ohm/sq. or less to said base sheet, said montmorillonite clay
comprising at least about 20 percent by weight of the total content
of clays and inorganic fillers.
2. The electroconductive paper base sheet of claim 1 wherein said
binder is present in the proportion of about 5 percent to about 200
percent by weight based on the total clay and filler content.
3. The electroconductive paper base sheet of claim 1 further
including a dielectric coating thereon whereby said paper is
adapted for electrographic printing.
4. The electroconductive paper base sheet of claim 1 wherein said
film-forming resinous binder is the coalesced residue of an aqueous
latex of said resinous polymer.
5. The electroconductive paper base sheet of claim 2 wherein said
montmorillonite clay is bentonite or fuller's earth.
6. The electroconductive paper base sheet of claim 2 wherein said
montmorillonite clay is present in the substantial absence of other
clays and other fillers.
7. The electroconductive paper base sheet of claim 3 wherein said
dielectric coating further contains a photoconductive material
dispersed therethrough.
8. The electroconductive paper of claim 7 wherein said
photoconductive material is zinc oxide.
9. In the method for forming an electroconductive paper base sheet
wherein a paper base sheet is coated with a conductive agent and an
insulating binder for said conductive agent, the improvement which
comprises;
coating said paper base sheet with a film-forming thermosetting or
thermoplastic resinous binder containing dispersed particles of
montmorillonite clay in a proportion sufficient for imparting a
resistivity of about 10.sup.9 ohm/sq. or less to said paper base,
and
curing the film-forming binder to form a binder film.
10. The method of claim 9 wherein said binder is present in the
proportion of about 5 percent to about 200 percent by weight based
on said montmorillonite clay.
11. The method of claim 10 wherein said binder is an aqueous latex
of a film-forming polymer.
12. The method of claim 11 further including the steps of applying
a coating mixture comprising a resin dispersion stabilized with a
fugitive base, said resin being a film-forming, acrylic acid resin
having an acid number in the range of about 25 to about 150, and
particulate photoconductive zinc oxide, and curing said resin to
form an insulating coating film containing photoconductive zinc
oxide dispersed therethrough.
13. An electroconductive paper for electrographic printing
characterized by good electrical conductivity over a wide range of
relative humidity comprising a paper base sheet having a continuous
coating of a clay of the montmorillonite type in admixture with a
styrene-butadiene copolymer or polyvinyl acetate or polyvinylidene
chloride latex binder, said binder being present in an amount of 5
to 200 percent by weight based on said clay.
14. An electroconductive paper for electrographic printing
characterized by good electrical conductivity over a wide range of
relative humidity comprising a paper base sheet having a continuous
coating of clay of the montmorillonite type in admixture with a
styrene-butadiene copolymer binder, said binder being present in an
amount of 5 to 200 percent by weight based on said clay.
15. The paper of claim 13 in which said clay is bentonite and said
binder is a copolymer of styrene and butadiene containing over 5
percent by weight of butadiene.
16. The paper of claim 14 in which binder is present in the amount
of 25 to 100 percent by weight based on said clay.
17. An electrostatic recording sheet for printing copies by
electrostatic reproduction which comprises an electroconductive
cellulosic base sheet having a coating of an admixture of
montmorillonite clay and styrene-butadiene copolymer binder, and an
electrostatic surface coating consisting essentially of
photoconductive zinc oxide and a panchromatic sensitive dye
dispersed in a polymeric binder film of an acrylic acid resin said
resin having an acid number in the range of about 25 to about
150.
18. The sheet of claim 17 in which said surface coating also
contains aluminum oxide.
19. The sheet of claim 18 in which said surface coating contains
from 5 to 30 percent of acrylic resin solids, 0.005 to 0.01 percent
dye and 5 to 25 percent of aluminum oxide, all percentages having
been based by weight upon the zinc oxide.
20. The sheet of claim 17 in which said dye is bromphenol blue.
Description
This invention relates to the manufacture of paper which is adapted
for the electrophotographic reproduction of images. It relates more
particularly to paper having unique electroconductive
properties.
In the preparation of paper and other cellulosic webbed base
materials adapted for electrographic printing, it has previously
been difficult to find satisfactory electroconductive substances
which are favorably adapted for the critical needs of good
electroconductivity, especially at low relative humidities, and
which can be readily applied from aqueous media to paper in usual
ways.
The moisture content of paper and, hence, its electrical
conductivity is determined by the relative humidity of its
environment. Thus, it has been shown that ordinary paper has a
resistivity of about 10.sup.14 ohm/sq. at 5 percent relative
humidity and about 10.sup.7 ohm/sq. at 95 percent relative
humidity. It has also been shown, and is well known by those
skilled in the art, that paper carrying a photoconductive surface,
i.e., zinc oxide in an insulating binder, will not readily
dissipate a negative charge from its surface to ground on exposure
to light if the paper base has a resistivity much greater than
about 10.sup.9 ohm/sq. Hence, while an ordinary paper base carrying
a photoconductive surface may perform satisfactorily with the type
of copy machines in which the papers are more or less automatically
processed at high relative humidity, the product may be absolutely
useless under dry conditions. It is for this reason that conductive
agents are added to electrophotographic base papers.
In the prior art, several methods of obtaining conductivity have
been used. One method consists of adding a humectant such as
glycerine or glycol. At the low range of humidities satisfactory
conductivity is obtained; however, at the high range of humidities
the conductivity is generally much higher than needed and tends to
cause problems in this respect and furthermore, at the high
humidities the sheet tends to become wet and extremely limp.
Hydroscopic salts such as lithium chloride have been proposed and
while they give somewhat better results than the humectants, they
are still subject to similar disadvantages. Water soluble
conductive polymers have been proposed such as polymerized
vinylbenzyl trimethyl ammonium chloride. While these materials show
some advantages over the former substances, they suffer from the
disadvantage of relatively high cost. None of the above mentioned
conductive agents are suitable if the zinc oxide or other
photoconductor is applied from an aqueous media using water soluble
or water dispersible insulating binder materials since the water
soluble conductive agent would migrate into the zinc oxide layer
and so reduce its resistance that electrostatic charging and,
hence, formation of an electrostatic latent image would be
impossible to attain.
It has been discovered in accordance with the present invention
that particulate montmorillonite clays in an aqueous synthetic
resin latex system when applied as a coating on a conventional
kraft or sulfite sheet of paper or other cellulosic webbed base
sheet produce an electroconductive paper that possesses good
electroconductivity at low relative humidities. It has further been
found that a paper web so treated is equally well suited for
application of zinc oxide or other photoconductors from the
conventional hydrocarbon solvent systems or photoconductive
formulations applied from aqueous dispersions to give useful
products for electrostatic printing. The clay coatings of the
instant invention are further characterized by their very low
cost.
Furthermore, the montmorillonite clay can be bound by conventional
paper pigment binders such as gelatins, cellulose ethers and
esters, casein and starch in conventional clay to binder
proportions, although these binders tend to be water sensitive and
therefore are not preferred when the photoconductor is to be
applied from an aqueous system. It has also been observed that base
paper containing montmorillonite clay bound with gelatins,
cellulose esters and ethers, casein, and starch are somewhat less
conductive than comparable base sheets prepared with latex binders,
but nevertheless, the papers using montmorillonite/conventional
binders are much more conductive than similar papers which do not
contain montmorillonite.
In addition to latex binders and conventional binders mentioned
above, other film-forming resinous binders such as thermosetting
and thermoplastic coating materials can be used as a binder for the
montmorillonite.
The montmorillonite clay minerals are complex hydrated aluminum
silicates containing traces of alkali and alkaline earth metals
such as sodium, magnesium and calcium along with other associated
impurities such as iron and silica. Some common designations for
minerals in the montmorillonite group are bentonite and fuller's
earth. It is not clearly understood why the montmorillonite clays
function to give the superior results in conjunction with the
photoconductors; however, it is thought that possibly they may
function as solid proton doners. We do not, however, wish to limit
the function of the specific clay to any special theory.
Kaolin type clays and other pigments such as titanium dioxide,
calcium carbonate, barium sulfate and the like are commonly
utilized as paper coating pigments in combination with various
adhesives, dispersing agents and stabilizing agents. These
materials do not enhance the conductivity of the paper base
although they can be present in the base sheet if they are required
for color, strength, appearance or some other reason. These
conventional materials merely function as "inerts" with respect to
conductivity. Conductivity can be obtained through the use of
montmorillonite clay even in the presence of such conventional
materials, although these materials may function as "diluents" and
detract somewhat from the conductivity. For attaining
conductivities suitable for commercial electrostatic printing
applications the montmorillonite content should be at least about
20 percent by weight of the total content of clays and inorganic
fillers and pigments. Usually, the content of such other clays and
fillers is minimized. Preferably, montmorillonite clay is used in
the substantial absence of other clays and fillers. This will be
further explained in the examples. Similarly, it is well known to
those skilled in the art that montmorillonite clays are not
considered suitable for conventional pigmented printing paper
coatings for many reasons such as poor rheological characteristics,
difficulty of obtaining sufficient coating weight, etc. Hence, no
commercial utilization of these clays in the huge coated printing
paper industry exists.
The binding vehicle for the montmorillonite clay is not
particularly critical as long as the binding material is compatible
with the montmorillonite and capable of curing to a uniform coating
film containing dispersed montmorillonite on the paper base. Curing
as used herein means that the binding vehicle forms a film on
drying, heating, calendering or otherwise processing. Curing does
not necessarily infer crosslinking exclusively but can include
coalescence as upon drying a latex. The film-forming binding
material, of course, must be substantially unaffected by any
overcoating composition (i.e., photoconductive insulating coating
or merely a dielectric coating not containing a photoconductor as
disclosed in Canadian Pat. No. 643,783, the teaching of which is
incorporated by reference) that may be subsequently applied.
For instance, when a photoconductive insulating coating is applied
from an aqueous coating composition the film-forming binder for the
montmorillonite should not be water soluble or otherwise water
sensitive so as to prevent migration of the conductive
montmorillonite into the insulating top coating. Similarly, the
film-forming montmorillonite binder should not be organic solvent
sensitive when an insulating top coating is applied from an organic
solvent.
Suitable film-forming binder vehicles include the natural or
conventional paper pigment binders such as casein; glues, gelatin;
starch; polyvinyl alcohol; gums and cellulose esters and ethers
(e.g., carboxyl methyl cellulose, sodium carboxylmethyl cellulose,
cellulose acetate and hydroxy ethyl cellulose). Some of these
binders tend to be water sensitive or water soluble and, therefore,
are not usually used when the conductive paper base is to be
overcoated with an aqueous coating composition.
Other suitable film-forming binders include the conventional
thermoplastic and thermosetting resinous polymers (including
homopolymers, copolymers, terpolymers, etc.), resinous coatings
such as polyolefins (e.g., polyethylene, oxidized or emulsifiable
polyethylene, and polypropylene); natural or synthetic waxes such
as carnauba wax and petroleum wax; modified or unmodified
polyesters (e.g., the ethylene glycol/maleic/phthalate styrene type
and glycerol phthalate type including those known as alkyds);
shellac; petroleum resins; natural resins; epoxide resins (e.g.,
diglycidyl ethers of bisphenol A and its homologs); silicone
resins; urea-formaldehyde resins; melamine-formaldehyde resins;
phenol formaldehyde resins; allyl resins; polystyrene resins;
polyamides such as nylon; vinyl resins such as polyvinyl chloride,
polyvinylidene chloride, polyvinyl acetate,
polyvinyl-chloride-polyvinyl acetate resins, vinyl chloride-styrene
resins, vinyl chloride-butadiene resins, vinyl
chloride-acrylonitrile resins; acrylic acid and acrylic ester
polymers such as polymethyl methacrylate, methyl
methacrylate-styrene; acetal polymers and copolymers; chlorinated
rubber; acrylonitrile-butadiene-styrene polymers; isoprene
polymers; butadiene-styrene copolymers; polyvinyl butyral resin;
styrene-ethylene copolymers; polyfluoroethylene resins,
polyvinylidene fluoride resins and polyurethane resins. These
resins can be in the form of solvent solution (e.g., in aromatic
hydrocarbons such as toluene and xylene; aliphatics such as hexane,
octane or even cycloaliphatics such as cyclohexane; or even in
solution in a vinyl monomer polymerizable with ethylenic
unsaturation present in the film-forming resins), water solution or
aqueous latex depending on chemical and physical properties of the
particular resins and the particular application for the
electroconductive paper prepared therefrom.
For application to the paper base, a slurry or dispersion of
montmorillonite clay in the resin solution, suspension or latex is
prepared according to conventional techniques for preparing clay in
binder dispersions such as disclosed in U.S. Pat. No. 3,028,258 the
teaching of which is incorporated by reference. The montmorillonite
clay to binder ratio is not particularly critical as long as there
is sufficient montmorillonite to provide a resistivity of less than
about 10.sup.9 ohm/sq. in the deposited coating. If the
montmorillonite to binder ratio is too high the clay will not be
securely held in place and the paper will tend to be chalky. When
the montmorillonite to binder ratio is too low, the conductivity
will suffer as a result of an excess of insulating binder.
Satisfactory results are obtained when the binder is present in the
proportion of about 5 percent to about 200 percent by weight based
on the montmorillonite clay. For efficiency and economy the binder
is present in the proportion of about 25 percent to about 100
percent by weight based on clay. When other clays or fillers are
present in addition to the montmorillonite the binder is present in
the proportion of 5 to 200 percent (and preferably 25 to 100
percent) by weight based on the total clay and filler content.
Preferably other clays and inorganic fillers are substantially
absent and montmorillonite clay is the only clay present.
The montmorillonite/binder coating composition can be applied to
the paper base by conventional coating means, such as spray
coating, roller coating, dip coating, air doctoring and the like in
dry coating weights of from about 5 lb./ream and lower to 20
lb./ream and higher (based on 500 sheets 25 .times. 38 inches per
ream). Also, the coating can be provided in the form of a film if
resinous material containing montmorillonite clay is laminated onto
the surface of the base sheet, as represented by the lamination of
a film of polyethylene containing dispersed montmorillonite onto
the paper base sheets.
Film-forming latex binders for montmorillonite clays are mentioned
above in conjunction with a preferred practice of the invention.
Latex or latices are colloidal suspensions of synthetic polymers as
prepared by emulsion or suspension polymerization. These latices
are preferred montmorillonite binders for use in conjunction with
aqueous photoconductive top coating for economy and efficiency
because the cured latex binder is not sensitive to the aqueous
photoconductor coating and there is no migration of montmorillonite
from the conductive base coat to the insulating photoconductive top
coat. Furthermore, the latices are not burdened with the cost
disadvantages and safety hazards associated with organic solvent
coating systems. Occasionally, montmorillonite clay will
destabilize certain latices prior to application of the paper
coating. This problem can be remedied by the addition of
conventional latex stabilizer as discussed below.
Several latices suitable for use in the present invention are
available commercially. These include butadiene-styrene latices
(Latex 512R, Dow Chemical) containing 35-55 percent total solids;
vinyl chloride latices containing 50-55 percent total solids;
vinylidene chloride-acrylonitrile copolymers (Saran F122-A15, Dow
Chemical); polystyrene latices containing 35-45 percent solids;
vinyl ester latices such as polyvinyl acetate containing 40-55
percent total solids (Gelva S-55, Shawinigan); latices of polyvinyl
acetate-polyvinyl chloride (Resyn 2507, National Starch) containing
40-50 percent total solids; butadiene-acrylonitrile copolymers
(Hycar 1577, Goodrich); styrene-acrylonitrile latices, polymethy
methacrylate latices and butadiene-acrylic ester latices. The
latices usually have an average molecular weight in the range of
about 25,000 to about 100,000.
In most synthetic latices, surface active materials are used in the
emulsion polymerization to prevent the agglomeration of particles
by maintaining a hydrophilic surface. There is a minimum protection
requirement for storage latex stability and additional protection
is required in the case when the latex is to be blended with
montmorillonite clays. Stability can be varied by changing the
amount of surface active material in a given latex. The stabilizer
requirement for a specific application depends primarily on the
particle size and the application, type of polymer, type of
stabilizer, pH and compounding ingredients. Control of latex
stability and coagulability can be controlled by additional
stabilizers when formulating the montmorillonite coating
composition.
There are four types of surface active stabilizers used for this
purpose: fatty acid soaps, rosin soaps, alkyl aryl sulfonates,
alkyl sulfates and other anionics with broad pH range and non-ionic
agents stable to a wide range of chemical compounds. These surface
active stabilizers can be supplemented with a small amount, i.e.,
less than 1 percent of the coating composition, of protective
colloid materials such as polyvinyl alcohols, casein, soya protein,
cellulose ethers and esters (i.e., carboxyl methyl cellulose,
hydroxyl ethyl cellulose), gums and starches. Other common
suspension stabilizers include finely divided inorganic
precipitates such as magnesium phosphate and potassium
pyrophosphate. In general, these suspension stabilizers serve the
purpose of lowering the interfacial tension between the dispersed
and continuous phases. Additionally, antifloccuating agents such as
Tamol-N which is a sodium salt of a condensation product of
formaldehyde and .beta.-naphthalene sulfonic acid sold by Rohm and
Haas Company can be used for additional stability.
Electroconductive base paper containing montmorillonite in a binder
as discussed above provide excellent substrates for receiving
photoconductive insulating top coatings as disclosed in U.S. Pat.
Nos. 2,959,481; 3,052,539 and 3,431,106 the teachings of which are
incorporated by reference.
For use in the instant invention, we have found that the binder
that gives superior results for binding the montmorillonite clay to
the paper substrate is an aqueous dispersion of a styrene-butadiene
copolymer latex containing from about 15 to 85 percent butadiene
and is advantageously employed as a base paper for "Electrofax"
printing at relative humidities of 25 percent or lower. Other
preferred synthetic resin lattices which are operable in place of
the styrene-butadiene copolymer are polyvinyl acetate and
polyvinylidene chloride latices.
Suitable styrene-butadiene latices can be obtained under various
brand names such as:
Latex 3820 and Latex 630 produced by Dow Chemical Co.
Ucar Latex 110 produced by Union Carbide Chemicals Corp.
Dylex Latex produced by Koppers Co., Inc.
Montmorillonite clays in particulate form can be obtained under
various brand names such as:
Wyo-Jel produced by Archer-Daniels Midland Co.
Volclay produced by American Colloids Co.
Bentolite produced by Georgia Kaolin Co.
Albertabond produced by National Lead Co.
As mentioned above, electrophotographic recording sheets have been
made by coating an electroconductive substrate, usually paper, with
a solution of an insulating resin such as silicone or polyvinyl
acetate in an aromatic hydrocarbon solvent such as toluene. The
finely divided photoconductor is suspended in this solution.
Satisfactory results are obtained when the ratio of photoconductor
to binder resin solids is within the range of 1:1 8:1 with a
coating thickness in the range of 0.2 to 1 mil. A preferred
photoconductor is zinc oxide for economy and efficiency. Other
photoconductors such as the oxides of aluminum, antimony, bismuth,
cadmium, lead, mercury, molybdenum, the iodides, selenides,
sulfides or tellurides of these metals; sulfur, anthracene,
selenium, polyvinyl carbazole and the like are also suitable for
the present invention.
Apparatus required for the application of such organic solvent
systems are usually costly, are subject to fire and health hazards.
While the organic solvent coating procedures result in
electrophotographic recording sheets that give excellent
reproduction of images, they suffer generally from poor adhesion of
the photoconductive layer to the electroconductive substrate, high
cost and the problems of applying the coating as mentioned
above.
Attempts heretofore made to apply the photoconductor to a paper
substrate from an aqueous medium resulted in generally
unsatisfactory performance. A major problem in former aqueous zinc
oxide photoconductive coatings has been drastically diminished
electrical insulating properties with consequent high dark decay.
General overall print quality was also not comparable to the
commercially available "Electrofax" papers produced with the
solvent systems.
According to another aspect of the present invention
electroconductive base papers containing montmorillonite in a
coalesced latex binder are overcoated with a dispersion of
photoconductive materials such as sulfur, selenium, cadmium
sulfide, polyvinyl carbazole, but preferably zinc oxide in an
aqueous solution of acrylic resin. The acrylic resin contains
sufficient carboxylic acid functionality to be "water solubilized"
(i.e., stably dispersed in water) by neutralization with a base.
The base used is a volatile or fugitive base such as ammonia or
other amino base (i.e., a primary, secondary or tertiary amine,
rather than a fixed alkali metal or alkaline earth metal hydroxide)
so that no appreciable ionic residues result from the decomposition
of the base during the curing of the photoconductive insulating
coating. A substantial proportion of ionic residues in the
photoconductive coating would, of course, have a detrimental effect
on performance.
The photoconductor can be any conventional photoconductor such as
those mentioned above that is compatible with the acrylic resin
solution. Photoconductive zinc oxide is preferred for efficiency
and economy. Suitable photoconductive zinc oxides are commercially
available under the names Photox 80 and Photox 801 (sold by New
Jersey Zinc Co.); PC 321, PC 331, and PC 340 (sold by St. Joseph
Lead Co.), and ZZZ-66-1 (sold by American Zinc Smelting Co.).
The acrylic resins suitable for the present purposes are those
resinous film-forming polymers (the term "polymers" as used herein
includes homopolymers, copolymers, terpolymers, etc.) containing
carboxylic acid functionality in an amount sufficient to provide
the polymer with an acid number in the range of about 25 to about
150. At acid numbers below 25 "water solubility" is not readily
achieved upon neutralization with a base. At acid numbers above 150
there is the possibility of an undesirable interaction with the
zinc oxide.
Compositionally, the acrylic acid resins can be an addition polymer
of acrylic acid and any vinyl monomer or monomers copolymerizable
therewith. Suitable vinyl monomers for polymerization with acrylic
acid to form the acrylic polymers include acylic esters such as
methyl acrylate, butyl acrylate, methyl methacrylate, 2 ethyl hexyl
acrylate, hydroxypropyl methacrylate, ethyl acrylate and the like;
aromatic monomers such as styrene and vinyl toluene; vinyl
chloride; ethylene; vinylidene chloride; lower alkyl (C.sub.1
-C.sub.4) substituted acrylic monomers (i.e., those having carboxyl
groups contributed by .alpha., .beta.-unsaturated carboxylic acids
or residues thereof, etc.) and so on. Also included are the acrylic
interpolymers disclosed in U.S. Pat. No. 2,767,153 such as the
interpolymers of 2-ethyl-hexyl acrylate-styrene-acrylonitrile and
methacrylic acid.
These resinous, film-forming, acrylic polymers are water
solubilized by neutralization or partial neutralization with a
water soluble, volatile, amino base such as ammonia, hydroxyl
amines, polyamines and monoamines such as monoethanolamine. Typical
amino bases include hydroxy amines, polyamines and monoamines such
as: monoethanolamine, diethanolamine, triethanolamine, N-methyl
ethanolamine, N-aminoethylethanolamine, N-methyl diethanolamine,
monoisopropanolamine, diisopropanolamine, triisopropanolamine,
"polyglycol amines" such as HO(C.sub.2 H.sub.4 O).sub.2 C.sub.3
H.sub.6 NH.sub.2, hydroxylamine, butanolamine, hexanolamine,
methyldiethanolamine, octanolamine, and alkylene oxide reaction
products of mono- and polyamines such as the reaction product of
ethylene diamine with ethylene oxide or propylene oxide,
laurylamine with ethylene oxide, etc.; ethylene diamine, diethylene
triamine, triethylene tetramine, hexamethylene tetramine,
tetraethylene pentamine, propylene diamine, 1,3 diaminopropane,
imino-bis-propyl amine, and the like; and mono-,di- and tri-lower
alkyl (C.sub.1-8) amines such as mono-, di- and triethyl amine.
In addition to the photoconductor and acrylic binder the aqueous
coating composition contains sensitizing dyes such as Bromphenol
Blue, Rose Bengal and Fluorscein and adjunct materials such as
Aluminum Oxide, e.g., Hydral 710 made by Alcoa and a dispersing
agent for the pigment, e.g., Tamol 850 made by Rohm and Haas (a
sodium salt of polymeric carboxylic acid).
For optimum results, the photoconductive coating contains from 5 to
30 percent of the acrylic binder solids, 0.005 to 0.01 percent of
sensitizing dye, and 5 to 25 percent of aluminum oxide, all
percentages being by weight and based upon the zinc oxide.
The preferred electroconductive base, as described above consists
of paper coated with a montmorillonite clay dispersed in a latex
binder, the quantity of binder ranging from 5 to 200 percent by
weight of clay.
The bromphenol dye is the only essential dye required for
panchromatic sensitization of the zinc oxide photoconductor. The
other dyestuffs are optional and add only small improvement to the
image quality. This is contrary to the prior art and not readily
understood. It appears that the bromphenol blue has also a
synergistic effect in the instant invention system, enhancing its
quality.
The aluminum oxide gives considerable improved image smoothness and
eliminates pinholes in the solid black areas as well as giving good
smoothness in the gray areas. In this respect it is essential.
Incorporation of the dispersing agent for the pigment is
optional.
The following examples illustrate ways in which the principle of
the invention has been applied but are not to be construed as
limiting its scope. All parts are parts by weight and all
percentages are weight percentages unless otherwise indicated.
EXAMPLE 1
Part A--Preparation of the Electroconductive Paper Base
A sheet of 40 pounds per ream of a bleached kraft paper was coated
in a conventional roll coater with the following composition:
---------------------------------------------------------------------------
Ingredients Parts by Weight
__________________________________________________________________________
Bentonite Clay (Volclay) 100 Latex 3820 (50% solids)
butadiene-styrene copolymer 200 Water 1,000
__________________________________________________________________________
The paper picked up approximately 10 pounds per ream of coating
material. The coated paper was dried to coalesce the latex binder
to form a water resistant coating containing uniformly dispersed
montmorillonite clay particles. The coating paper had a resistivity
value well below 10.sup.9 ohm/sq.
Similar results are obtained using a butadiene-styrene
acrylonitrile latex (40 percent solids) or a butyl methacrylate
latex or polyvinyl chloride latex (50 percent solids), polyvinyl
butyral latex (35-45 percent solids), polyvinyl acetate latex
(40-50 percent solids) or polyvinylidene chloride latex in place of
butadiene-styrene latex 3820 used above.
Similar results are also obtained by depositing the montmorillonite
on the paper from a toluene solution of polystyrene resin; or a
methanol solution of shellac; or an acetone solution of vinyl
chloride-vinyl acetate copolymer, or an ethyl acetate-toluene
solution of nitrocellulose.
Part B--Deposition of a Photoconductive Coating From a Solvent
System on the Conductive Paper of Part A
A conventional solvent base zinc oxide "Electrofax" coating similar
to that described by C. J. Young and H. G. Greig in "Electrofax
Direct Electrographic Printing on Paper," "RCA Review," Vol. XV,
No. 4, pages 469, 484 (Dec. 1954) was applied to the paper with a
pickup of about 20 pounds per ream. After drying, the paper was
conditioned in the dark at 25 percent relative humidity and then
processed in an SCM Electrostatic Copy Machine Model 33 to produce
a copy of a typewritten document. A print of excellent contrast and
density resulted with no appreciable background.
Similar results are obtained using selenium, sulfur or cadmium
sulfide in place of zinc oxide as the photoconductor.
EXAMPLE 2
An electroconductive base paper of 50 pounds weight per ream (25
.times. 38 inches--500) made in accordance with part A of example 1
was coated with the following composition on a conventional air
knife coater and dried.
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Ingredients Parts by Weight
__________________________________________________________________________
Film-forming acrylic polymer solution * 60 Photox 801 Zinc Oxide 90
Hydral 710 Aluminum Oxide 10 Bromphenol Blue 0.006 Water 30
__________________________________________________________________________
* Film-forming acrylic polymer solution comprising an aqueous
solution containing about 30% of an ammonia neutralized, low
molecular weight, ethyl acrylate-methyl methacrylate-acrylic acid
terpolymer having the aforementioned monomeric components present
in the respective ratio of 65/27/8. The polymer also contains
hydroxyl functionality in the proportion of 1% to 2% of the
polymer. The polymer had an Acid Number of about 50-55. The polymer
had a weight average extended chain length (in Angstrom units) of
about 895.4 and a number average extended chain length (in Angstrom
units) of about 343.4. The polydispersity index (wt. average
extended chain length divided by no. average extended chain length)
was about 2.6.
The above composition when applied to give a coating weight of 20
to 40 pounds per ream produced a photoconductive copy sheet which
gave copy quality as to image density, gray scale, and speed equal
to conventional commercially available solvent coated products.
Prints of excellent quality were obtained at 25 percent relative
humidity. The copies were prepared using the commercial papers and
those of the invention on commercial electrostatic copy machines,
including
Scm machines, Models 33, 44, or 55
Charles Bruning "Copytron" 2000, 2001
Apeco "electrostat"
Similar results can be obtained using Carboset 514 acrylic resin
solution sold by B. F. Goodrich Company as the film-forming acrylic
binder.
EXAMPLE 3
PART A
A sheet of 40 pounds per ream of a bleached kraft paper was coated
with a rod coater with the following composition:
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Ingredients Parts by Weight
__________________________________________________________________________
Bentonite 100 Latex 630 (50% solids) 50 butadiene-styrene copolymer
Water 1,000
__________________________________________________________________________
The paper picked up approximately 10 pounds per ream of coating
material. The coated paper was dried to coalesce the latex binder
to form a water resistant coating containing uniformly dispersed
montmorillonite clay particles. The coated paper had a resistivity
value well below 10.sup.9 ohm/sq.
PART B
When coated with either the solvent base photoconductive zinc oxide
coating as described in part B of example 1 or the aqueous zinc
oxide coating as described in example 2 and a copy made on a
Charles Bruning Company Model No. 2000 Copytron Electrostatic
printing machine, copies of excellent density and contrast resulted
at 25 percent relative humidity.
EXAMPLE 4
The electroconductive paper prepared in part A of example 3 was
coated with a photoconductive coating composition similar to the
composition of example 2 except that the film-forming acrylic
polymer solution was an aqueous solution containing about 35
percent solids of an ammonia neutralized polymer of methyl
methacrylate/n-butyl acrylate/styrene/acrylic acid having an acid
number of about 75-80 and having the aforementioned monomeric
components present in the respective ratio of 40/35/15/10. The
polymer had a weight average extended chain length (in Angstrom
units) of about 941.5, and a number average extended chain length
(in angstrom units) of about 335.4. The polydispersity index (wt.
average extended chain length divided by no. average extended chain
length) was about 2.8.
The coating method was similar to that employed in example 2.
Photocopies of original documents were prepared on this paper
prepared in this example by the method of example 2 and excellent
quality photoreproductions resulted.
When the adhesive binders such as starch or casein are used to bind
the montmorillonite clay in the paper base, and this conductive
paper base is overcoated with a photoconductor in an insulating
binder from a non-aqueous coating composition, copies can be made
on a conventional electrostatic machine using papers coated
therewith; although the base papers are not as conductive as those
base papers utilizing the latex binders.
EXAMPLE 5
To demonstrate the use of conventional paper coating clays and
fillers with montmorillonite clay in producing electroconductive
paper, the following tests were conducted.
Coating A--Volclay brand bentonite clay (a type of montmorillonite
clay) was dispersed at 11.5 percent solids concentration in water
with 1 percent of a sodium hexametaphosphate dispersing agent,
(Calgon, sold by Calgon Company) based on bentonite together with
20 percent of a butadiene-styrene latex, Dow 630 (20 percent latex
solids based on bentonite).
Coating B--A conventional kaolin paper coating clay was dispersed
at 65 percent solids in water with 0.5 percent sodium
hexametaphosphate together with 20 percent butadiene-styrene latex,
Dow 630 (20 percent latex solids content based on clay).
Coating A and coating B were blended in various proportions to
provide various ratios of montmorillonite to kaolin as reported
below. Coating A, coating B and the various blends were
individually coated on ordinary bleached kraft papers having no
special previous treatment with a No. 32 rod coater. The coatings
were dried, calendered and conditioned for 2 hours at 50 percent
relative humidity and then conditioned overnight at 20 percent
relative humidity. The log of the resistivities of the coated
surfaces at 20 percent humidity were then determined and the
results are reported below:
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Ratio of Montmorillonite Log of the Resistivity in Clay to Kaolin
Clay ohm/sq. of the Coated Surface
__________________________________________________________________________
.infin. (coating A) 8.70 4:1 8.73 2:1 8.76 1:1 8.60 1:2 8.83 1:4
9.41 1:8 10.46 0 (coating B) 12.39
__________________________________________________________________________
the above data indicates that the log of the surface resistivity of
the coated surface decreases from 12.39 to 8.70 in going from 100
percent kaolin clay to 100 percent bentonite clay in the paper
coating. This data demonstrates that conventional pigments and
fillers can be used in conjunction with the montmorillonite clay in
electroconductive paper when these pigments and fillers are
required to obtain some property other than conductivity in the
paper. This data indicates that the montmorillonite content should
be at least about 20 percent by weight of the total clay and filler
content in order to achieve a resistivity of about 10.sup.9
ohm/sq.
If conductive agents of the type described and utilized in the
prior art were applied in place of the montmorillonite pigment, no
copy would result if the aqueous zinc oxide type of coating were
used as the photoconductive layer because of migration of the agent
into the zinc oxide layer which would result, as described
earlier.
The quantities of film-forming binder based on the clay are in the
range of 25-100 percent by weight of solids with maximum practical
limits of 5-200 percent. Coating weights of the electroconductive
clay coating can vary from 5-20 pounds per ream (25 .times. 38
inches--500).
While the use of the electroconductive composition of the present
invention is emphasized for use in the range of relative humidities
of 25 percent and less, good results are obtained also at relative
humidities above 25 percent.
To produce an aqueous coated paper for electrographic printing,
sometimes called "direct electrostatic printing," as described in
Canadian Pat. No. 643,783 issued June 26, 1962, to the A. B. Dick
Co., only a simple modification in the composition of our zinc
oxide coating is required. Since direct electrostatic printing, as
described in the above patent, requires a dielectric surface
coating on an electroconductive base, it was found that a coating
of a water soluble acrylic resin of the type described herein
(without zinc oxide) when coated on the electroconductive base as
described in part A of example 1 produces a product well suited to
the purpose. The electroconductive base is coated on a conventional
air knife coater from a 25 percent water solution of the special
acrylic resin to give a coat weight of 3 to 6 pounds per ream (25
.times. 38 inches--500). The prior art teaches that the dielectric
coatings must be applied from solvent systems, but we have found
that good results are obtained from this aqueous solution thus
eliminating all the disadvantages of working with an organic
solvent.
* * * * *