U.S. patent number 3,674,711 [Application Number 04/883,732] was granted by the patent office on 1972-07-04 for electrically conductive transparent plastic material.
This patent grant is currently assigned to Varian Associates. Invention is credited to John A. Dahlquist, Bert Growald, Guy A. Marlor.
United States Patent |
3,674,711 |
Growald , et al. |
July 4, 1972 |
ELECTRICALLY CONDUCTIVE TRANSPARENT PLASTIC MATERIAL
Abstract
An electrically conductive clear transparent self-supporting
plastic sheet consisting of a homogeneous solid molecular mixture
of a clear transparent conductive polymer and a film forming clear
transparent polymer is obtained by combining a quaternary ammonium
polyelectrolyte, such as polydimethyl diallyl ammonium chloride,
with a film forming polymer, such as polyvinyl alcohol, and a
mutual solvent, such as water. The mixture is then cast onto a
smooth surface, the mutual solvent evaporated, and the resultant
sheet material stripped from the casting surface to obtain a sheet
of electrically conductive clear transparent plastic material
useful as a conductive plastic or, after coating with a charge
retentive film, as an electrographic recording medium.
Inventors: |
Growald; Bert (Los Altos,
CA), Dahlquist; John A. (Palo Alto, CA), Marlor; Guy
A. (Santa Clara, CA) |
Assignee: |
Varian Associates (Palo Alto,
CA)
|
Family
ID: |
25383220 |
Appl.
No.: |
04/883,732 |
Filed: |
December 10, 1969 |
Current U.S.
Class: |
252/500;
260/DIG.18 |
Current CPC
Class: |
H01B
3/44 (20130101); H01B 1/122 (20130101); Y10S
260/18 (20130101) |
Current International
Class: |
H01B
1/12 (20060101); H01B 3/44 (20060101); H01b
001/00 (); C08d 009/06 (); C08f 029/12 () |
Field of
Search: |
;252/500
;260/2.1R,2.1M,2.1E,17,17.4,874,895,DIG.18 ;117/211 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Drummond; Douglas J.
Claims
What is claimed is:
1. An electrically conductive clear transparent self-supporting
plastic sheet comprising:
a homogenous solid molecular mixture of a clear transparent
conductive polymer and a film forming clear transparent
polymer;
the conductive polymer being a water-dispersible quaternary
ammonium polyelectrolyte consisting of at least one member selected
from the group consisting of
a. homopolymers of a vinylbenzyl quaternary ammonium compound
having the general formula:
wherein R, R' and R" each represents individually a monovalent
radical selected from the group consisting of CH.sub.2
OH--CH.sub.2, CH.sub.3 --CHOH--CH.sub.2, CH.sub.2
OH--CHOH--CH.sub.2 and alkyl, aryl, cycloalkyl and aralkyl
hydrocarbon radicals, and R, R' and R" collectively represent the
formula:
wherein the three valences are attached to the nitrogen atom, and Y
is an anion, said R groups containing a total of not more than 12
carbon atoms in the substituent radicals,
b. copolymers of at least two such vinylbenzyl quaternary ammonium
compounds,
c. copolymers of at least 65 percent by weight of at least one of
such vinylbenzyl quaternary ammonium compounds and not more than 35
percent by weight of acrylamide, and
d. copolymers corresponding to from 95.0 to 99.99 percent by weight
of at least one of such vinylbenzyl quaternary ammonium compounds
and from 5.0 to 0.01 percent by weight of divinylbenzene; and
the film forming polymer is at least one material selected from the
group consisting of, polyvinyl alcohol, agar,
carboxymethylcellulose, polyvinyl acetate, polyvinyl
acetate-alcohol copolymers, polyvinyl acetal, polyvinyl formal,
polyacrylic acid, methyl cellulose, and polyvinylpyrrolidone.
2. The apparatus of claim 1 wherein the film forming polymer is
polyvinyl alcohol.
Description
DESCRIPTION OF THE PRIOR ART
Heretofore, electrically conductive transparent films have been
prepared by combining a film forming polymer, a plasticizer for the
polymer, an electrolyte soluble in the plasticizer, and a solvent
for the polymer and casting the resultant mixture on a casting
surface to provide a self-supporting, transparent, electrically
conductive film. An example of such prior art is disclosed in U. S.
Pat. No. 3,357,930 issued Dec. 12, 1967. In this prior art
disclosure it was contemplated that a relatively wide range of
electrolytes, including acids, bases, or salts could be employed,
provided that the electrolyte was soluble in the plasticizer.
However, conductive films formed according to the aforecited prior
art do not appear to have the requisite stability when employed as
the conductive substrate for a clear transparent charge retentive
film of an electrographic recording web.
SUMMARY OF THE PRESENT INVENTION
The principal object of the present invention is the provision of
an improved electrically conductive transparent plastic material
which is perfectly colorless or non-light absorbing.
One feature of the present invention is the provision of a clear
transparent conductive plastic material having a conductive polymer
combined with a film forming polymer, whereby the improved
stability of the film forming polymer is imparted to the resultant
composite polmeric plastic material.
Another feature of the present invention is the same as the
preceding feature wherein the conductive polymer is a quaternary
ammonium polyelectrolyte.
Another feature of the present invention is the same as the first
feature wherein the conductive polymer is polypiperidinium
chloride.
Another feature of the present invention is the same as any one or
more of the preceding features including the provision of a clear
non-conductive plastic charge retentive film disposed overlaying
one major surface of a sheet of the conductive plastic material to
form an electrographic recording web.
Other features and advantages of the present invention will become
apparent upon a perusal of the following specification taken in
connection with the accompanying drawings wherein:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic flow diagram, in block diagram form,
depicting the method for making conductive plastic sheet according
to the present invention, and
FIG. 2 is a fragmentary perspective view, partly in section,
depicting an electrographic recording web employing features of the
present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIGS. 1 and 2, there is shown in block diagram
form the method for making the electrographic recording web 1 of
FIG. 2 which comprises a clear, transparent, conductive sheet, as
of 0.010 inch thick, having a clear, transparent, charge retentive
film 3, as of 4 microns thick, adhered to the clear conductive
sheet 2. Such an electrographic recording web is suitable for use
in electrophotography to provide a transparency of photographic
quality.
In the first step of the method, a film forming polymer, such as
polyvinyl alcohol, is combined with a conductive polymer, such as
polydimethyl diallyl ammonium chloride and a mutual solvent for
both polymers to form a clear, non-light absorbing, colorless
liquid comprising a homogenous mixture of the polymers in the
solvent, such as water. The mixture, in the next step, is cast as a
sheet onto a substrate to a uniform thickness, as of 0.040 inch
thick. In the next step, the solvent is evaporated to leave a
clear, non-light absorptive, transparent film, as of 0.010 inch
thick on the substrate. The film is then peeled from the substrate
to produce an electrically conductive, clear, non-light absorptive
transparent film which may be utilized as the clear conductive
sheet 2 of the electrographic recording web 1, or which may be
utilized for other applications where a transparent conductive
plastic sheet is desired. In the next step, the conductive sheet 2
is coated to a thickness, as of 4 microns, with a clear charge
retentive film such as of polyvinyl chloride-acetate and allowed to
dry, thereby producing the electrographic recording web 1 of FIG.
2.
The film forming polymeric material useful in the practice of this
invention includes a wide variety of polymers which are transparent
in sheets varying from thicknesses corresponding to 0.0001 inch to
1 inch. Aside from transparency, the polymer should be castable in
the form of a gel, as opposed to a hard, highly crossed linked
film, so as to allow ionic mobility, and its usefulness as a film
should not be effected by the continued presence of the solvent,
for example, water in the amounts required to effect ionization of
the electrolyte.
Among the film forming polymers particularly preferred in the
practice of this invention may be mentioned those which are
polymers of hydroxyl containing monomers, esters, or acetals.
Examples of such polymers include polyvinyl alcohol, agar,
carboxymethylcellulose, polyvinyl acetate, polyvinyl
acetate-alcohol, copolymers, polyvinyl acetal, polyvinyl formal,
acrylic resins, such as polyacrylic acid, methyl cellulose,
polyvinylpyrrolidone, CARBOSET 525 acrylic polymer and CARBOSET 514
acrylic polymer, the latter two being manufactured by B. F.
Goodrich Chemical Company, a division of the B. F. Goodrich
Company, 3135 Euclid Avenue, Cleveland 15, Ohio. It should be noted
that in describing the polymers as those of named monomers, it is
not implied that they are necessarily made by actual polymerization
of such monomers. Thus, for example, polyvinyl alcohol may be
described as a polymer of monomeric vinyl alcohol, but is
invariably produced by indirect means, as vinyl alcohol is
non-existent in fact.
The conductive polymer materials useful in the practice of this
invention include polymers which are transparent or nearly so in
thin films. The conductive polymers are capable of providing both a
source of ions and the necessary water-holding capacity
(hygroscopicity). Polyelectrolytes are particularly suited for this
application because of their ionic nature and ability to hold water
at low humidity. Particularly suitable polyelectrolytes include the
quaternary ammonium polyelectrolytes. The polymers of this type
include vinylbenzyl quaternary ammonium compounds and can be any
water-soluble or water-dispersible homopolymer or copolymer of one
or more vinylbenzyl quaternary ammonium compounds, or copolymers of
a predominant amount of vinylbenzyl quaternary ammonium compound
and a minor amount of a nonacidic copolymerizable compound such as
acrylamide, or copolymers containing, in the polymer molecules,
residues corresponding to from 95.0 to 99.99 percent by weight of
one or more vinylbenzyl quaternary ammonium compounds and from 5.0
to 0.01 percent by weight of divinyl benzene. More specifically,
the electroconductive substance can be a homopolymer or a copolymer
of any two or more vinylbenzyl quaternary ammonium compounds having
the general formula:
wherein R, R' and R" each represents individually a monovalent
radical selected from the group consisting of CH.sub.2 OHCH.sub.2,
CH.sub.3 CHOHCH.sub.2, CH.sub.2 OHCHOHCH.sub.2 and alkyl, aryl
cycloalkyl and aralkyl hydrocarbon radicals, and R, R' and R"
collectively represent the radicals of the formula:
wherein the three valences are attached to the nitrogen atom, the R
groups containing a total of not more than 12 carbon atoms in the
sum of the constituent radicals, or a copolymer of at least 65
percent by weight of any one or more of such vinylbenzyl quaternary
ammonium compounds with not more than 35 percent by weight of
acrylamide, or a copolymer containing, in the polymer molecules,
residues corresponding to from 95.0 to 99.99, preferably from 99.0
to 99.99 percent by weight of any one or more of such vinylbenzyl
quaternary ammonium compounds and from 5.0 to 0.01, preferably from
1.0 to 0.01, percent by weight, of divinylbenzene. Mixtures of any
two or more of the homopolymers or copolymers can also be used. The
polymers are of relatively high molecular weight and are
characterized by a viscosity of at least 2 centipoises for a 0.5
percent by weight solution of the polymer in an aqueous 2 percent
by weight solution of sodium chloride at 25.degree. C. as
determined by an Ostwald viscosimeter.
In the preferred embodiment of the invention the electroconductive
polymer is a homopolymer or copolymer of one or more vinylbenzyl
quaternary ammonium compounds having the aforementioned general
formula wherein R represents an alkyl radical containing from one
to four carbon atoms, R' and R" each represents a radical of the
group consisting or CH.sub.2 OHCH.sub.2, CH.sub.3 CHOHCH.sub.2,
CH.sub.2 OHCHOHCH.sub.2 and lower alkyl radicals containing from 1
to 4 carbon atoms and Y is an anion, e.g., a sulfate, a chloride, a
nitrate, or a hydroxyl ion, copolymers of at least 65 percent by
weight of any two or more such vinylbenzyl quaternary ammonium
compounds and not more than 35 percent by weight of acrylamide, or
copolymers of from 99.0 to 99.99 percent by weight of at least one
such vinylbenzyl quaternary ammonium compound and from 1.0 to 0.01
percent by weight of divinylbenzene. A particularly suitable
quaternary ammonium polymer is polypiperidinium chloride having an
integral heterocyclic ring as shown by the following general
formula: ##SPC1##
wherein the anion is a chloride and the polymer comprises a
homopolymer of disubstituted diallyl ammonium chloride monomers
where R and R' are selected from the groups consisting of methyl,
ethyl, and methyl, ethyl, butyl and octyl, respectively. A
particular one of the aforementioned polypiperidinium chlorides is
polydimethyl diallyl ammonium chloride marketed by Calgon
Corporation of Pittsburgh, Pennsylvania, as conductive polymer No.
261.
Mutual solvents useful in the practice of this invention include
water methanol-water mixtures.
In order to illustrate more fully the nature of the invention and
the manner of practicing same, the following examples are
presented.
EXAMPLES
A castable composition is prepared by dissolving 15 percent by
weight polyvinyl alcohol in water. A suitable grade of polyvinyl
alcohol is ELVANOL grade 70-05 available from E. I. DuPont de
Nemours & Company, Inc., Organic Chemicals Department. This
grade of polyvinyl alcohol is a hot-water-soluble grade and is
slurried in cold water and then heated to complete solution. More
particularly, add to the vessel the required amount of water at
75.degree. F. or below and start agitation. Sift the polyvinyl
alcohol into the vortex such that it is rapidly worked out and
dispersed and stir this way for 10 minutes. Raise the temperatures
to 194.degree. F. or above and continue stirring at
194.degree.-203.degree. F. until the resin is completely dissolved,
usually about 30-60 minutes. To the dissolved polyvinyl alcohol add
polydimethyl diallyl ammonium chloride (conductive polymer 261
manufactured by Calgon Corporation) in the proportions 20 parts by
weight to each 100 parts by weight of dry polyvinyl alcohol. The
conductive polymer is preferably added in a 40 percent water
solution, i.e., 40 percent by weight conductive polymer in water
and stirred into the polyvinyl alcohol until dispersed uniformly
therein. The solution is coated on a glass plate or other suitable
substrate. The coating on the glass plate substrate is obtained by
spreading a pool of the solution on the substrate with a glass rod
to obtain a uniform thickness for the coating of approximately
0.040 inch. The coated substrate is then put in an oven at
170.degree.to 180.degree. F. and heated until dry, typically about
30 minutes. Upon drying, the coating reduces to a thickness of
approximately 0.010 inch. When dry the coated substrate is removed
from the oven and allowed to cool to room temperature. Upon cooling
to room temperature, the coating is stripped or peeled from the
substrate to obtain the clear, transparent, conductive plastic
sheet of the present invention.
In the aforecited specific example, a 25 percent solution of QX
3521 polymeric quaternary ammonia salt made by Dow Chemical Company
may be substituted for polydimethyl diallyl ammonium chloride. The
sheet 2 is perfectly clear, sufficiently flexible for further
processing, and surprisingly resistant to finger marks, moisture or
stickiness. The bulk conductivity of the sheet 2 was approximately
10.sup.7 ohm centimeters when tested in ambient conditions
(20.degree. C. and 50percent relative humidity).
The amount of conductive polymer to be employed will depend to some
extent upon the degree of conductivity desired. As a general rule,
however, it can be said that the amount of conductive polymer
should be in the range between 5 percent and 50 percent by weight
of the film forming polymer.
To make an electrographic recording web, the cast sheet, after
drying on the substrate, is coated with a dielectric charge
retentive film as of vinyl chloride-acetate to a thickness as of 4
microns. If desired, the sheet 2 may be then stripped from the
substrate or prepared in rolls or the like after the manner of
making cellophane and similar films to provide a self-supporting,
transparent electrically conductive sheet with a charge retentive
film adhered thereto.
Since many changes could be made in the above construction and many
apparently widely different embodiments of this invention could be
made without departing from the scope thereof, it is intended that
all matter contained in the above description or shown in the
accompanying drawings shall be interpreted as illustrative and not
in a limiting sense.
* * * * *