U.S. patent number RE28,543 [Application Number 05/520,077] was granted by the patent office on 1975-09-02 for electroconductive paper.
This patent grant is currently assigned to Calgon Corporation. Invention is credited to Jerry E. Boothe, Merwin Frederick Hoover.
United States Patent |
RE28,543 |
Boothe , et al. |
September 2, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Electroconductive paper
Abstract
Electroconductive paper useful typically in making copies by an
electrosatic process is made by incorporating therein a polymer
comprising at least 90% monomers of the formula ##EQU1## where R is
an alkyl group of one to 18 carbon atoms and R.sub.1 is R or
.beta.-propionamido and A is an anion.
Inventors: |
Boothe; Jerry E. (Pittsburgh,
PA), Hoover; Merwin Frederick (Topsfield, MA) |
Assignee: |
Calgon Corporation (Pittsburgh,
PA)
|
Family
ID: |
27060042 |
Appl.
No.: |
05/520,077 |
Filed: |
November 1, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
743634 |
Jul 10, 1968 |
03544318 |
Dec 1, 1970 |
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|
Current U.S.
Class: |
428/514; 162/138;
427/391; 427/121; 430/62 |
Current CPC
Class: |
D21H
19/12 (20130101); G03G 5/107 (20130101); Y10T
428/31906 (20150401) |
Current International
Class: |
D21H
19/00 (20060101); D21H 19/12 (20060101); G03G
5/10 (20060101); B44D 001/00 (); G03G 007/00 () |
Field of
Search: |
;96/1.5
;117/155UA,201,161 ;427/121,391 ;428/514 ;162/138
;260/29.7,80.3,88.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lusignan; Michael R.
Attorney, Agent or Firm: Anderson, Jr.; Rudolph J. Westlake;
Harry E. Katz; Martin L.
Parent Case Text
RELATED APPLICATION
This is a continuation-in-part of our copending application, Ser.
No. 462,742 filed June 9, 1965, now abandoned.
Claims
We claim:
1. Electroconductive paper including a layer of
poly-[N-methyl-N-(.beta.-propionamido)-3,5-methylene piperidinium
chloride].
2. Electroconductive paper including a layer of
poly-(N,N-dimethyl-3,5-methylene piperidinium chloride).
3. Electroconductive paper including a layer of
poly-(N,N-dimethyl-3,5-methylene piperidinium chloride) crosslinked
with from about 0.1% to about 1% methylenebisacrylamide, based on
the weight of the polymer.
4. Electroconductive paper containing about 0.1 to about 3.0 pounds
per 3000 square feet of at least one water-soluble polymer
comprising at least 90% by weight groups of the formula ##EQU11##
where R is an alkyl group containing one to .[.eighteen.].
.Iadd.four .Iaddend.carbon atoms, R.sub.1 is selected from the
group consisting of R and ##EQU12## and A is an anion. .[. 5. Paper
of claim 4 in which the water-soluble polymer contains up to 10% by
weight diallyl amine of the formula (CH.sub.2 =CH--CH.sub.2).sub.2
NY where Y is an alkyl group of up to 18 carbon atoms..]. .[. 6.
Paper of claim 4 in which the water-soluble polymer contains up to
10% by weight groups of the formula ##EQU13## where R.sub.2
represents a member of the class consisting of hydrogen, halogen,
and alkyl groups of one to four carbon atoms, and R.sub.3
represents a radical of the class consisting of aryl and alkaryl
radicals and radicals represented by the formulas ##EQU14## where
R.sub.5 and R.sub.6 each represents a radical selected from the
class consisting of alkyl, cycloalkyl, and alkoxyalkyl radicals,
R.sub.7 has the same meaning as R.sub.5 and R.sub.6 and, in
addition, an aryl radical, R.sub.8 and R.sub.9 each represents a
member of the class consisting of hydrogen, and alkyl, cycloalkyl,
aryl, alkaryl, aralkyl, and alkoxyalkyl radicals and R.sub.10 has
the same meaning as R.sub.5 and
R.sub.6..]. 7. Paper of claim 4 in which the polymer includes up to
about 10% by weight units derived from the group consisting of
acrylamide, diacetone acrylamide, N-methylolacrylamide, and N-vinyl
2-pyrrolidinone.
Paper of claim 4 in which the polymer includes up to about 10
weight percent of a water soluble polyethylenically unsaturated
monomer branching
agent. 9. Paper of claim 8 in which the water soluble
polyethylenically unsaturated monomer is selected from the group
consisting of methylene bisacrylamide, triallyl amine hydrohalide
salts, tetrallyl ammonium salts, and triallyl ammonium salts
including an alkyl group of 1 to 4 carbon
atoms. 10. Electroconductive paper containing at least about 0.1
pound per 3000 square feet of at least one water-soluble polymer
consisting essentially of units derived from monomers of the
formula ##EQU15## where R is an alkyl group of one to .[.18.].
.Iadd.four .Iaddend.carbon atoms and R.sub.1 is selected from the
group consisting of R and ##EQU16##
11. Paper of claim 10 in which the polymer consists essentially of
units
derived from dimethyl diallyl ammomium chloride. 12.
Electroconductive paper containing at least about 0.1 pound per
3,000 square feet of at least one water-soluble polymer derived
from polymerization of a monomer mix of (a) monomers of the formula
##EQU17## where R is an alkyl group of one to 18 carbon atoms,
R.sub.1 is selected from the group consisting of R and
.beta.-propionamido, and (b) up to about 10% by weight of a
water-soluble copolymerizable branching agent.Iadd.selected from
the group consisting of polyallyl substituted polyalcohols,
polyallyl substituted polyamine hydrohalides and quaternary salts,
and N,N'-methylene bisacrylamide. .Iaddend. .[. 13. Paper of claim
12 in which the branching agent is selected from the group
consisting of polyallyl substituted polyalcohols, polyallyl
substituted polyamine hydrohalides and quaternary salts, and
N,N'-methylene bisacrylamide..].
Method of making electroconductive paper comprising incorporating
therein at least about 0.1 pound per 3,000 square feet of a
water-soluble polymer consisting essentially of repeating units
derived from dimethyl
diallyl ammonium chloride. 15. Method of making electroconductive
paper comprising incorporating in said paper about 0.1 to about 3.0
pounds, per 3,000 square feet of paper, of water-soluble polymer
comprising at least 90% by weight groups of the formula ##EQU18##
where R is an alkyl group of one to .[.18.]. .Iadd.four
.Iaddend.carbon atoms and R.sub.1 is selected from the group
consisting of R and ##EQU19##
16. Method of claim 15 in which the polymer contains a
cross-linking
agent. 17. Method of claim 15 in which the polymer contains a
branching
agent. 18. Method of claim 15 in which the polymer is a homopolymer
of dimethyl diallyl ammonium chloride and is incorporated to the
extent of at
least 0.5 pound per 3,000 square feet of paper. 19. Method of claim
15 in which the polymer is added to the paper in the form of an
aqueous
solution. 20. Method of claim 15 in which a solution of polymer is
formed into a layer on the paper and subsequently dried.
Description
BACKGROUND OF THE INVENTION
This invention relates to paper containing electroconductive
materials. In particular, it relates to paper rendered
electroconductive by a layer or coating of electroconductive
material, which paper is useful in various copying processes and
devices.
Electroconductive paper may be used to distribute electrical
stresses in various insulating products; see U.S. Pat. No.
3,148,107. Where electrically conductive paper is to be used for
nonimpact printing, a substrate, backing, impregnation coating, or
layer of electrically conductive material is usually constructed.
See Vaurio and Fird, "Electrically Conductive Paper for Nonimpact
Printing," Tappi, December 1964, vol. 47, No. 12, pp. 163A-165A.
Various types of nonimpact printing processes are known as
electrostatographic, electrophotographic, electrographic,
"Electrofax," and other processes. As a rule such processes call
for the placement of an electric charge on the paper, which may be
accomplished by a corona discharge, for example. The charge is, in
most such processes, placed on the paper in darkness. The paper may
also contain a photo-responsive or photo-conductive layer or
material, now popularly a specially treated zinc oxide, which
causes the charge to be dissipated in an area where light strikes
it, thus leaving a pattern of the charged areas which is a
reproduction of the image desired. The charged area attracts a
powdered or other usually particulated image-forming material which
may be fused or otherwise treated to make the image permanent.
Other processes differ in that the image is created by electrical
dissipation of the static charge in nonimage areas; in this and
other processes (see Vaurio and Fird, supra), the common
characteristic is an electrically conductive base paper.
Probably the most common system at present is the direct
electrostatic process; see "Chemical & Engineering News," July
20, 1964, pp. 88-89; U.S. Pat. No. 3,052,539. This process is
similar to the xerographic method of copy reproduction; however,
the conductive substrate is built into paper rather than being on a
separate drum or other device.
Among the desirable characteristics of an electrically conductive
material for use in nonimpact printing are whiteness and stability
of conductivity over a wide range of relative humidity. Various
inorganic additives have been rejected or criticized by workers in
the art because of their excessive weight and/or objectionable
color as well as their poor tolerance of humidity variations. The
organic polymers suggested by Silvernail and Zembal, U.S. Pat. No.
3,011,918, have objectionable odors and tastes result in
objectionable background colorations on the paper.
SUMMARY OF THE INVENTION
Our invention is useful in imparting electroconductive
characteristics to the paper for use in such processes as the
above.
We have discovered that the class of water-soluble polymers
containing at least about 90% repeating groups of the formula
##EQU2## where R is an alkyl group containing one to eighteen
carbon atoms, R' is selected from the group consisting of R and
##EQU3## and A is an anion, may be used in making electroconductive
paper. Any water-soluble polymer of this description is within the
scope of our invention.
The preferred homopolymer of the described class is derived from
free radical polymerization of dimethyl diallyl ammonium chloride.
The polymerization method described by Butler and Angelo, "Journal
of American Chemical Society," vol. 79, p. 3128 (1957), may be used
satisfactorily to make polymers which perform in our invention.
Also useful in the homopolymer of the monomer diallyl methyl
.beta.-propionamido ammonium chloride. Other polymers useful in our
invention are included in the description of Butler's U.S. Pat. No.
3,288,770.
Diallyl ammonium monomers undergo cyclization during free radical
polymerization to form piperidinium rings. The homopolymer of
dimethyl diallyl ammonium chloride may be described as a
polydimethyl-3,5-methylene piperidinium salt. The homopolymer of
diallyl methyl .beta.-propionamido ammonium chloride, for example,
is known as poly [N-methyl-N(.beta.-propionamido) 3,5-methylene
piperidinium chloride].
Thus, polymers containing repeating groups of Formula I may be
derived from polymerization of monomers of the formula ##EQU4##
where R is an alkyl group of one to 18 carbon atoms, R.sub.1 is
selected from the group consisting of R and .beta.-propionamido,
and A.sup.- is an anion.
Anions which are particularly of interest are fluoride, chloride,
bromide, hydroxide, nitrate, acetate, HSO.sub.4.sup.- and H.sub.2
PO.sub.4.sup.-.
Water-soluble copolymers and more complex polymers of the
above-described monomers containing at least about 90% of Formula I
repeating groups are contemplated within the scope of our
invention. Any copolymerizable monomer which will form a
water-soluble polymer with the diallyl monomer may be used for the
remaining 10%. Among the monoethylenically unsaturated
copolymerizable monomers suitable for use in our invention are
acrylamide, diacetone acrylamide, N-vinyl pyrrolidinone, and
N-methylolacrylamide. We prefer to use as the comonomer with the
diallyl quaternary ammonium compounds, a compound which is
copolymerizable therewith and which is represented by the general
formula ##EQU5## or, after polymerization, as ##EQU6## where R
represents a member of the class consisting of hydrogen, halogen,
R' and alkyl groups of one to four carbon atoms, and R' represents
a radical of the class consisting of aryl and alkaryl radicals and
radicals represented by the formulas ##EQU7## where R.sub.5 and
R.sub.6 each represents a radical selected from the class
consisting of alkyl, cycloalkyl, and alkoxyalkyl radicals, R.sub.7
has the same meaning as R.sub.5 and R.sub.6 and, in addition, an
aryl radical, R.sub.8 and R.sub.9 each represents a member of the
class consisting of hydrogen, and alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, and alkoxyalkyl radicals, and R.sub.10 has the same
meaning as R.sub.5 and R.sub.6. See Schuller and Thomas U.S. Pat.
No. 2,923,701 for a description of the mechanism of
copolymerization of such monomers with the diallyl quaternary
ammonium compounds discussed above. See also Schuller et al.,
"Journal of Chemical & Engineering Data," vol. 4, p. 273
(1959).
We may also use diallyl amine monomers which are preferably
copolymerized in the form of a hydrohalide salt. See Butler,
Angelo, and Cranshaw, U.S. Pat. No. 2,926,161. They may be
described in terms of the formula ##EQU8## where R is an alkyl
group of one to four carbon atoms or .beta.-propionamido, and
A.sup.- is a halide anion.
Also contemplated in our invention is the use in paper of the
above-described homopolymers and copolymers having included in
their polymerized structures certain compatible polyethylenic
unsaturated compounds. Such polyethylenic unsaturated compounds,
when present in small amounts (i.e., up to about 10%) during the
polymerization of a dialkyl diallyl ammonium halide monomer, cause
the resulting polymer to be highly branched and/or cross-linked.
The branched polymer also imparts superior barrier properties to
the paper substrate preventing solvent from the application of the
photoconductive upper layer from diffusing into the paper. The
preferred branching agents are methylene bisacrylamide, triallyl
amine hydrohalide salts, triallyl quaternary ammonium salts having
as a fourth group an alkyl group of one to four carbon atoms, and
tetraallyl ammonium salts. However, we may use any water soluble,
polyunsaturated compound which is copolymerizable with the diallyl
monomers previously described. Polyallyl sucrose and other allyl
substituted polyalcohols may be used, as well as polyallyl
polyamine hydrohalides and quaternary salts. The amount of each of
these branching agents required to get the desired results varies
with each compound, the only requirement being that irreversible
(water-insoluble) gel formation should be avoided. As little as
0.001% of such branching agent will significantly improve the film
forming ability of the polymer. Preferred ranges are between about
0.01 percent and 0.1 percent.
As is known in the art of electrostatic printing and other forms of
nonimpact printing, conductivity measurements for conductive
coatings on paper may be made on the conductive areas only; that
is, the electrodes of the conductivity device may be simply
attached to the conductive surface of the paper. Generally
speaking, papers adapted for use in various types of nonimpact
printing may have surface resistivities in the range of about 2.5
.times. 10.sup.5 to about 3.0 .times. 10.sup.9. Molecular weights
of our polymers are apparently not critical to conductivity.
The following examples illustrate not only the utility of our
invention in electroconductive paper, but also the conductivity of
the paper at various relative humidities. The indicated changes in
conductivity with relative humidity are comparatively excellent in
the present state of the art.
EXAMPLE I
A 4% by weight aqueous solution of a copolymer of dimethyl diallyl
ammonium chloride and methyl dodecyl diallyl ammonium chloride in
the molar ratio of 17.5 to 1 was applied to Bergstrom Paper
Company's Indsen No. 1 raw coating stock (basis weight 46 lbs. per
3,300 square feet) using a 3 mil, wire-wound Meyer rod. This rod
applies approximately 0.3 lb. of pure polymer per 3,000 square feet
of paper. The sample was then dried in an oven at 105.degree. C.
for 20 to 30 minutes. An 8 square inch circular sample was cut and
placed into a constant conditions room for 16 hours at 50% relative
humidity and 72.degree. F. After this period, the sample was
conditioned for 72 hours at 23% relative humidity. Current
measurements were made after applying 100 v. DC using Keithley
equipment consisting of a Model No. 240 Regulated High Voltage
Supply, a Model No. 6105 Resistivity Adapter and a Model 610--B
Electrometer. The resistivity adapter is suitable for determining
both surface and volume resistivities. Electrodes are constructed
of stainless steel; however, for measurements at relative
humidities of greater than 70% a special graphite center electrode
was used. Current readings were converted to obtain resistivity
values. The surface resistivity of this polymer was 5.9 .times.
10.sup.3 ohms/square.
EXAMPLE II
Poly(N,N - dimethyl-3,5-methylene piperidinium chloride) was
prepared in aqueous solution and applied to a paper by a Time-Life
bench coater. Two pounds of polymer covered an area of 3,000 sq.
ft. After drying, conductivity measurements showed the following
surface resistances at the relative humidities indicated in terms
of ohms/square: ##EQU9## Using the same polymer in a concentration
of three pounds per 3,000 sq. ft., the following surface
resistances were found: ##EQU10##
EXAMPLE III
In another test in which two pounds of our preferred homopolymer
was spread on 3,000 sq. ft. of paper, the conductivity results,
measured in terms of surface resistance, were virtually identical
to a polymer disclosed in U.S. Pat. No. 3,011,918. There were no
objectionable odor or background discoloration in the paper treated
with the polymers of our invention.
EXAMPLE IV
A 4% by weight aqueous solution of poly (methyl .beta.-propionamido
diallyl ammonium chloride) was applied to the test paper as above.
After treatment as in Example I, this paper gave a surface
resistivity value of 2.0 .times. 10.sup.10.
EXAMPLE V
A 4% by weight solution of a copolymer of dimethyl diallyl ammonium
chloride (93% by weight) acrylamide (4%) and acryonitrile (3%) was
applied and treated as in Example I. At a relative humidity of 12%,
the surface resistivity was 8.6 .times. 10.sup.10.
EXAMPLE VI
A 4% by weight solution of a copolymer of dimethyl diallyl ammonium
chloride (96% by weight) and acrylonitrile (4%) was applied and
treated as in Example I. At a relative humidity of 16%, the surface
resistivity was 1.8 .times. 10.sup.10.
EXAMPLE VII
A 4% by weight solution of a copolymer of dimethyl diallyl ammonium
chloride (95% by weight) and diacetone acrylamide 5% was applied
and treated as in Example I. The surface resistivity at 24 %
relative humidity was 3.6 .times. 10.sup.9.
EXAMPLE VIII
A 4% solution of homopolymer of diethyl allyl ammonium chloride was
applied and treated as in Example I. The surface resistivity at 20%
relative humidity was 7.9 .times. 10.sup.11.
EXAMPLE IX
A 4% by weight solution of a copolymer of dimethyl diallyl ammonium
chloride copolymerized with 0.03 weight percent methylene
bisacrylamide was applied and treated as in Example I. The surface
resistivity at 23% relatively humidity was 1.8 .times.
10.sup.10.
EXAMPLE X
A 4% solution of dimethyl diallyl ammonium copolymerized with 0.12
weight percent tetraallyl ammonium chloride was applied and treated
as in Example I. The surface resistivity at 23% relative humidity
was 1.4 .times. 10.sup.10.
Solutions of our polymers may be applied to paper or cellulosic
webs by coating, diping, brushing, wet end addition, etc.
Concentrations of the polymer may vary widely to fit the method of
handling. Generally about 0.5-3.0 pounds of polymer should be
applied per 3,000 sq. ft. but for some purposes as little as 0.1
pound will provide sufficient conductivity. The upper limit of
addition will be determined largely by economics; so far as we are
aware, there is no upper limit which is or will be detrimental to
the electroconductive character of the paper.
We do not intend to be limited to the specific examples and
illustrations employed in the preceding description of our
invention. It may be otherwise variously practiced within the scope
of the following claims.
* * * * *