U.S. patent number 3,655,527 [Application Number 05/071,718] was granted by the patent office on 1972-04-11 for electrolytic printing using polyvinyl alcohol.
This patent grant is currently assigned to Bell Telephone Laboratories, Incorporated. Invention is credited to Robert Kyran Curran, Robert Eugene Kerwin, Theodore Arthur Shankoff.
United States Patent |
3,655,527 |
Curran , et al. |
April 11, 1972 |
ELECTROLYTIC PRINTING USING POLYVINYL ALCOHOL
Abstract
Hard copy prints are produced by an electrolytic scanning
process. Free iodine is generated in the printing sheet at the
writing electrode and reacts with colorless polyvinyl alcohol (PVA)
in the 5,000 to 500,000 molecular weight range to produce optically
dense colored spots. The color depends upon the molecular weights
of the vinyl alcohol polymers present.
Inventors: |
Curran; Robert Kyran (Stirling,
NJ), Kerwin; Robert Eugene (Westfield, NJ), Shankoff;
Theodore Arthur (Mendham, NJ) |
Assignee: |
Bell Telephone Laboratories,
Incorporated (Murray Hill, NJ)
|
Family
ID: |
22103128 |
Appl.
No.: |
05/071,718 |
Filed: |
September 14, 1970 |
Current U.S.
Class: |
205/53; 346/25;
427/145; 427/434.2; 346/135.1 |
Current CPC
Class: |
B41M
5/20 (20130101) |
Current International
Class: |
B41M
5/20 (20060101); B21h 001/20 () |
Field of
Search: |
;204/2,18PC
;117/36.7 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Trifariello; T.
Claims
What is claimed is:
1. Process for the electrolytic production of a print comprising
the selective electrolyzing of a printing sheet characterized in
that the said printing sheet contains an intimate physical
combination of an iodide salt and at least one polymer of vinyl
alcohol in the molecular weight range from 5,000 to 500,000.
2. A printing sheet comprising a sensitizing material characterized
in that the said sensitizing material comprises an intimate
physical combination of an iodide salt and at least one polymer of
vinyl alcohol in the molecular weight range from 5,000 to
500,000.
3. A printing sheet of claim 2 in which the said sensitizing
material comprises 1 .times. 10.sup. 17 to 1 .times. 10.sup. 20
molecules of the said iodide salt and 0.001 to 0.03 gram of the
said at least one polymer of vinyl alcohol per square centimeter of
the said sheet.
4. A printing sheet of claim 2 in which the said sensitizing
material comprises sufficient water to make the said sheet
electrically conductive.
5. A printing sheet of claim 3 in which the said sensitizing
material comprises ethylene glycol.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
Facsimile prints are produced from transmitted electrical
signals.
2. Description of the Prior Art
There are, in the electrolytic facsimile art, several classes of
writing processes. In one general class, metallic ions from one of
the electrodes are introduced into the printing sheet and there
either combine with colorless materials already present in the
printing sheet in order to form colored complexes, or are
precipitated as fine metallic particles. In another general class
of writing processes the electrodes are not consumed, the writing
being accomplished by the electrolytic modification of materials
already in the printing sheet. A process of this latter type
involves the starch-iodine reaction. In this process electrolysis
of potassium iodide in the paper generates free iodine which reacts
with the starch, also present in the paper, producing the widely
known purple starch-iodine complex. The process is fairly sensitive
requiring moderately low currents to produce a sufficiently dense
image. However, it is not sufficiently stable when exposed to light
or in file storage to be considered a permanent record.
SUMMARY OF THE INVENTION
For the electrolytic production of a print from transmitted
electrical signals, it has been found that the use of polyvinyl
alcohol (PVA) in the molecular weight range from 5,000 to 500,000
in place of starch, used in a prior art printing process involving
the electrolysis of an iodide salt, yields a more sensitive
printing sheet which produces prints of greatly increased
permanence. In addition, the prints can be produced in any desired
color by selecting the molecular weight or combination of molecular
weights of the vinyl alcohol polymers incorporated in the printing
sheet. The colors range from red at the lower end of this molecular
weight range through the visible spectrum to blue at the upper end
of this molecular weight range.
In the disclosed writing process PVA and an iodide salt are
incorporated together with an electrolyte in the printing sheet. A
writing head scans the printing sheet and selectively electrolizes
portions of the sheet. This electrolysis generates free iodine from
the iodide salt. This iodine complexes with the colorless PVA to
form the colored image. The electrolyte is required to impart
electrical conductivity to the printing sheet and ionize at least a
portion of the iodide salt. Water can be used to form the
electrolyte or such materials as polymers of ethylene glycol in the
molecular weight range 300 to 2,500.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE is a schematic view of an exemplary electrolytic
printing apparatus.
DETAILED DESCRIPTION OF THE INVENTION
The disclosed printing process depends upon the presence in the
printing sheet of three classes of constituents at the time
printing is to take place. An iodide salt (usually an inorganic
water soluble salt) is required for the formation of free iodine.
Polyvinyl alcohol (PVA) is required as the complexing agent which
forms the colored record. Finally, an electrolyte is required to
impart electrical conductivity to the printing sheet and ionize at
least a portion of the iodide salt. FIG. 1 shows a roll 10
dispensing a printing sheet 11 which passes around rollers 14
through a liquid 12 and then through the writing head 13. The
writing head 13 is activated by the electrolytic signal source 15
which causes the writing head 13 to selectively electrolyze the
printing sheet 11 in accordance with information derived from a
source of information 16 which may be local or remote.
The three necessary classes of constituents described above can be
present in the printing apparatus 1 in several different places.
The three constituents can all be incorporated in a presensitized
roll 10, in which case the liquid 12 is not necessary, or any of
the three constituents can be introduced within the apparatus 1 as
the printing sheet 11 passes through the liquid 12.
The writing head 13 can contain, for instance, a single electrode
pair which scans mechanically back and forth the paper as the paper
moves through the writing head 13 or it can contain an array of
electrodes which are electronically scanned by logic circuitry
contained in the electrolytic source 15. The voltage levels
required for the disclosed printing process fall in the 2 to 10
volt range which is easily controllable by solid state
circuitry.
The iodide salt used is usually an inorganic water soluble salt
such as potassium iodide. When current passes between the writing
electrodes some of the iodide ions present in the paper are iodized
at the cathode to form iodine. This iodine rapidly complexes with
PVA in the region with very little lateral migration. A resolution
of 20 lines per millimeter has been observed. This resolution is
more than adequate for facsimile reception since a resolution of 5
lines per millimeter is all that is required to resolve elite type.
The iodide salt should be present in the printing sheet in a
concentration of at least 10.sup. 15 molecules per square
centimeter in order to produce an image. However, at least 10.sup.
17 is preferable. Any desired higher concentration can be used.
However, it should not be necessary to use more than 10.sup. 20
molecules per square centimeter under ordinary circumstances.
The color of the PVA-iodine complex depends upon the molecular
weight of the vinyl alcohol polymers present. Vinyl alcohol
polymers with molecular weights of the order of 5,000 give a red
complex. As the molecular weight of the polymer is increased, the
dominant color of the complex moves through the spectrum until near
a molecular weight of 500,000 the blue end of the spectrum is
reached. Mixtures of vinyl alcohol polymers will yield the various
subtractive mixture colors according to well-known principles. The
colors produced include brown or grey which can be used to provide
a conventional black and white printed appearance. PVA should be
present in the printing sheet in a concentration of at least 0.001
gram per square centimeter in order to yield a sufficiently dark
image. Any desired higher concentration can be used. However,
concentrations greater than 0.03 gram per square centimeter give
the sheet an overly gelatinous feel.
The electrolyte can be formed by simply including water in the
printing sheet. The amount of water required depends upon the
desired operating voltage. The drier the printing sheet, the higher
the voltage required to print. However, an amount of water
sufficient for printing at a 2 volt level will just give the paper
a damp feel. As stated above, the water can be included in the
presensitized printing sheet 10 or can be introduced at some point
12 within the printing apparatus 1.
Other electrolytes can be used to meet particular device
requirements. For instance, if it is desired to store rolls 10 of
presensitized printing sheet, polyethylene glycol in the molecular
weight range of 300 to 2,500 can be used as an electrolyte. The
glycol has a very low vapor pressure so that the presensitized
rolls have a long shelf life. The useful range of ethylene glycol
polymers is limited at the low end by increasing volatility and at
the high end by increasing stiffness. Operation in the molecular
weight range of 350 to 2,000 yields preferable results.
Polyethylene glycol is sufficiently hygroscopic to retain a small
amount of water originally introduced or to absorb a small amount
of moisture from the atmosphere.
EXAMPLE
The preparation of a sensitized printing sheet, according to the
disclosed invention, can be accomplished by the following
procedure:
The preparation of a sensitized printing sheet, according to the
disclosed invention, can be accomplished by
a. prepare a 10.sup.-.sup.3 molar to 1 molar aqueous iodide
solution containing 1/2 percent to 10 percent PVA;
b. immerse in this solution a sheet of good quality bond paper;
c. remove the paper; and
d. allow the paper to dry in a room with relative humidity greater
than 15 percent.
This sensitization process causes the deposition in the paper of 1
.times. 10.sup. 17 to 1 .times. 10.sup. 20 molecules of iodide salt
per square centimeter and 0.001 to 0.03 gram of PVA per square
centimeter.
The sheet is now in condition for writing. Writing can be done by
placing the sheet on a conducting plate and applying 1 to 10 volts
between a 10.sup..sup.-3 inch diameter metal pin and the conducting
plate, then drawing the pin across the sheet.
* * * * *