U.S. patent number 3,775,115 [Application Number 05/162,708] was granted by the patent office on 1973-11-27 for method of preparing lithographic printing plate.
This patent grant is currently assigned to Addressograph-Multigraph Corporation. Invention is credited to Lawrence H. Frischkorn, Percy M. Kay, Jack L. Sorkin.
United States Patent |
3,775,115 |
Sorkin , et al. |
November 27, 1973 |
METHOD OF PREPARING LITHOGRAPHIC PRINTING PLATE
Abstract
The printing plate and process for preparing the same described
herein comprises a printing plate suitable for dry lithography
having in the non-image producing areas an ink repellent coating
such as a cured elastomeric organopolysiloxane and in the ink
receptive image producing areas the same cured elastomeric
organopolysiloxane coated with a fused toner, and having under said
organopolysiloxane layer a base which may be of various materials.
In a preferred process for preparing this printing plate, the base
is an electrophotographic sheet which is given an electrostatic
charge which serves as the means for attracting and holding the
toner imposed on the polysiloxane layer until the toner image is
fused onto the polysiloxane layer. In another modification an image
of toner is imprinted on one base and then the toner image is
superimposed and transferred to the organopolysiloxane coating and
the toner fused to make it ink receptive.
Inventors: |
Sorkin; Jack L. (University
Heights, OH), Kay; Percy M. (Chesterland, OH),
Frischkorn; Lawrence H. (Bratenahl, OH) |
Assignee: |
Addressograph-Multigraph
Corporation (Cleveland, OH)
|
Family
ID: |
22586804 |
Appl.
No.: |
05/162,708 |
Filed: |
July 14, 1971 |
Current U.S.
Class: |
430/49.2;
101/457; 101/462; 101/466; 430/66; 430/302 |
Current CPC
Class: |
B41N
1/003 (20130101); G03G 13/286 (20130101) |
Current International
Class: |
B41N
1/00 (20060101); G03G 13/28 (20060101); G03f
007/02 (); G03g 005/00 (); G03g 007/00 () |
Field of
Search: |
;96/33,1.8
;101/465,466,467,457,462 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Klein; David
Claims
What is claimed is:
1. A planographic printing plate capable of being imaged, having
oleophobic non-image and oleophilic image areas, and is suitable
for accepting oil-base ink only in the image areas and printing
therefrom, while rejecting the oil-base ink in the non-image areas,
comprising:
an electrophotographic base comprising a flexible support over
which is applied a photoconductive layer;
an oleophobic layer superimposed on said electrophotographic base
and adhered thereto which is highly repellent to said oil-base ink
when dry, said oleophobic layer being further characterized as
comprising a cured elastomeric organopolysiloxane having a ratio of
organic groups to silicon atoms in the range of about 1.95:1 to
about 2.1:1 and having an adhesive release value, when dry, of less
than about 100 grams per inch; an oleophilic layer of fused toner
in the image areas of said printing plate, superimposed on and
adhered to said oleophobic layer, whereby said printing plate
selectively accepts said oil-base ink in the image areas and repels
said oil-base ink from the non-image areas.
2. The plate of claim 1 in which said electrophotographic base is
zinc oxide-coated.
3. The printing plate of claim 1 in which said oleophobic layer
comprises a cured elastomeric polymer of dimethyl polysiloxane.
4. The printing plate of claim 3 having a release value of less
than 30 grams per inch.
5. The process of preparing a lighographic plate comprising the
steps of:
superimposing on an electrophotographic base a coating of an
oleophobic material comprising a cured elastomeric
organopolysiloxane having a ratio of organic groups to silicone
atoms in the range of about 1.95:1 to about 2.1:1 and having an
adhesive release value, when dry, of less than about 100 grams per
inch;
drying and curing said oleophobic coating by heating at a
temperature in the range of 30.degree.C -200.degree.C;
applying a blanket electrostatic charge to the surface of said
electrophotographic base;
exposing said charged surface to a pattern of light and shadow;
superimposing on said oleophobic coating an image corresponding to
said pattern of light and shadow formed with a toner material
comprising a pigment and an organic binder; and
heating said superimposed image at a temperature in the range of
89.degree.C - 10.degree.C thereby fusing and permanently affixing
the toner composition to said oleophobic surface.
6. The process of claim 5 in which said electrophotographic base is
zinc oxide dispersed in a resin binder.
7. The process of claim 5 in which said toner material is applied
by superimposing the image on said electrostatically charged
electrophotographic base coated with said oleophobic coating,
exposing said image to actinic light for at least one-half second
thereby dissipating the electrostatic charge on said coated base in
the areas under the non-image areas and retaining the electrostatic
charge on the said coated base under the image areas; then applying
a toner suspended in a liquid medium to said coated base whereby
the toner particles are retained and adhered in electrostatically
charged areas of said base and not being retained in those areas no
longer electrostatically charged; and heating said toner-bearing
areas at a temperature in the range of 100.degree.-130.degree. C.
whereby said toner is fused and permanently affixed to said ink
repellent surface.
Description
BACKGROUND OF THE INVENTION
This invention relates to planographic printing. More specifically,
it relates to lithographic printing which does not require water or
dampening solutions applied in the non-image areas to prevent the
printing ink from depositing in these non-image areas. Still more
particularly, it relates to planographic plates and printing in
which the non-image areas comprise a layer of material which itself
repels the printing ink and the image producing areas comprise a
layer of fused toner which has been deposited and retained on the
otherwise repellent surface by means of a charge retained by an
electrophotographic base positioned between the layer of repellent
material, with the toner being subsequently fused and permanently
affixed to the repellent layer.
RELATED PRIOR ART
Lithographic printing has been a widely accepted and well
recognized part of the printing art for many years. This is based
on the principle that water is coated over the non-image areas of a
printing surface and when ink is imposed on the printing surface it
is retained only in the areas which have not been wet with water,
whereas the water-wet areas reject the oil-based printing ink.
There are many problems associated with this type of printing, such
as back-flowing, the requirement for high quality paper stock,
control of the delicate balance between ink and fountain solution
in order to maintain image fidelity and uniformity, the need for
constant attention to guard against changes in printing as
conditions change on the press during the course of a printing
run.
The desire and need for improvements in this art are evidenced by
the number of patents issued in this field, many of which are
directed to reducing the amount of water needed and otherwise
controlling the quality of printing produced by such processes.
Typical of these patents are U.S. Pat. Nos. 1,406,837, 1,817,522,
2,090,704, 2,381,704 and 3,025,789.
The Curtin Patent No. 3,511,178 discloses the use of a cured
elastomeric organopolysiloxane layer in the non-image areas to
repel the printing ink and having the organopolysiloxane etched
away in the image areas, or altered in these areas by electrical
discharge to remove from the image areas the material or the
property of the material which will repel printing ink. The etching
operation is found to be rather cumbersome and requires very
careful control to maintain fidelity and accuracy in reproducing
the image. The electrical discharge method is found to be much less
effective than the etching operation.
STATEMENT OF THE INVENTION
In accordance with the present invention, it has been found that
the image area of the organopolysiloxane layer can be more easily
and more accurately reproduced by having under this layer an
electrophotographic base which will allow the composite sheet to be
charged electrostatically and to hold onto the cured elastomeric
organopolysiloxane layer a toner reproduced image which can be made
permanently receptive to printing ink by fusing the toner into
position. Most surprisingly it has been found that coating of the
electrophotographic base with the polysiloxane elastomer does not
destroy or interfere with the ability of the electrostatic base to
retain the electrostatic charge.
In one modification, the desired image, such as a photographic
positive, is superimposed on the base on which an electrostatic
charge has been imposed by corona discharge, and upon exposure of
the image to light the electrostatic charge is dissipated in the
non-image areas and retained only in the desired image areas. The
toner powder is then applied to the entire surface of the printing
area. The toner is rejected in the non-image areas and retained in
the image areas. Then the toner is fused permanently in place in
accordance with conditions normally used for the particular toner
and the fused toner thereby becomes ink receptive and capable of
printing the desired image.
In a second modification, the toner is not directly imposed on the
repellent polysiloxane surface, but the image is placed on a
separate, independent electrostatically charged master, exposed to
light and the toner applied to such separate master to reproduce
the image with toner particles positioned in the image areas. Then
the electrostatic base which is coated with the ink repellent
organopolysiloxane coating is given an electrostatic charge over
its entire surface. The toner image on the separate master is
thereafter superimposed on the organopolysiloxane surface with the
toner image in contact with the repellent surface, and by hand
applied to roller applied pressure is transferred to that surface.
The electrostatic charge on the siloxane-coated base attracts and
holds the toner so that it is transferred to the polysiloxane
surface. Then the image toner is fused and permanently affixed to
the polysiloxane surface so that the image areas now become
receptive to printing ink.
In a third modification, the second modification is repeated except
that the base on which the silicone coating is applied does not
have an electrostatic charge and the toner image is transferred
from the transfer sheet and its toner image are superimposed on the
ink repellent surface.
In still another modification the silicone coating can comprise a
mixture of the polysiloxane and zinc oxide. The amount of zinc
oxide in range from 0 percent to 60 percent by weight with the
balance of the coating material comprising the silicone or
polysiloxane material. The preferred mixture is about 50 percent by
weight of each of the two components.
The expression "toner" as used herein is well known in the
electrostatic printing art and refers to a pigment, either organic
or inorganic, coated with a binder, generally a resin, and carrying
an electrostatic charge so that it is attracted to a sheet or
master having an opposite electrostatic charge in the image area,
or less frequently in the non-image area, to which the toner
particles are to be deposited. When toner particles have been
appropriately applied in the desired areas, heat is applied to fuse
the binder material and thereby permanently affix the toner in
position.
Particularly effective materials found to function as ink repellent
surfaces are cured, solid, rubbery organopolysiloxanes. There are
also known as "silicone elastomers" formed by continued
polymerization or curing of silicone "gums" achieved by heating in
the temperature range of 30.degree.C to 200.degree.C. A
particularly useful commercial product is General Electric's
RTV-108.
Specific silicone gums can be used having the linear repeating unit
##SPC1##
There may be as few as two such repeating units or as many as
20,000 or more. The R groups may be identical or may be different,
but they are selected from the class consisting of monovalent alkyl
or aryl radicals, halogenated alkyl or aryl radicals, cyanolkyls. A
small proportion of these may be vinyl, phenyl, halogenated vinyl,
halogenated phenyl and the like. While other alkyl groups, up to 10
carbon atoms, may be used, and preferably a methyl group. The end
groups in the polymers may be ##SPC2##
wherein Ac is a saturated aliphatic monoacyl radical having no more
than 10 carbon atoms, preferably no more than four carbon
atoms.
Silicone elastomers, formed by continuing the polymerization of the
gums just referred to, are characterized generally as very sparsely
crosslinked dimethylpolysiloxanes of high molecular weights, that
is about 400,000-800,00 average molecular weight. These sparsely
crosslinked polymers are indicated by R/Si ratios very close to 2,
generally above 1.95, or even above 1.99, but generally below 2.1,
or even below 2.01. Generally there are 200-500 dimethyl units
between crosslink sites. In contrast, the much more densely
crosslinked silicone resins found suitable for commercial use have
R/Si ratios in the range of 1.2 - 1.5.
The silicone gums are preferably compounded with catalysts for
promotion of cure, and also with fillers, such as silica, to
improve the chemical properties. Available commercial silicone gums
generally provide satisfactory repellency on curing. These also
have superior mechanical properties which minimize wear caused by
physical handling and by the abrasive conditions encountered on the
press. The gum may be filled or unfilled. A particularly effective
non-filled silicone gum is General Electric's silicone gum SE-76
having an average molecular weight of 400,000 - 500,000 and curing
to an elastomeric satisfactorily repellent surface.
In evaluating materials as to being sufficiently ink repellent,
such as the silicone elastomers described herein, it has been found
that the repellency increases directly as the "release value"
decreases. The effectiveness of a release agent surface is measured
by recognized test by applying a piece of adhesive tape, such as
surgical tape, to the surface and thereafter measuring the amount
of force required to strip the adhesive tape from the surface.
In determining the "release value," an "Instron" Model TM is
employed, which operates at a crosshead speed of 12 inches per
minute and chart speed of 2 inches per minute. One inch Johnson
& Johnson "Red Cross" brand, waterproof adhesive tape is used,
selecting only a roll having a retention force of about 450 grams
(425-475) as measured at 80.degree. F. on a 24-gauge, No. 4 finish
stainless steel test panel. In determining either the retentive
force of the tape to be used or the release value of a sample, a
10-inch strip of tape is applied to a 6-inch by 1 1/2 inch panel by
passing a 4 1/2 pound rubber-faced tape roller twice over the tape,
using only the weight of the roller. The sample is immediately
placed in the Instron and the force in grams determined necesary to
strip the tape at an angle of 180.degree..
The amount of force required to strip the tape is referred to as
the "release value," and the larger the release value, the more
adhesion there is between the adhesive tape and the surface. A
small release value indicates a very effective release coating or a
high repellency, and a large release value indicates a very
ineffective release coating or low repellency. Standard tests for
release value are described in TAPPI (Technical Association for the
Pulp and Paper Industry), Vol. 43, No. 8, Pages 164A and 165A
(August, 1960) and TAPPI Routine Control Method (not a TAPPI
standard) RC-283 "Quality of Release Coatings" issued in 1960.
The General Electric RTV-108 described herein has a release value
of 12 grams per inch and the SE 76 has a value of 1 gram per inch.
Suitable silicone elastomer surfaces have been found to have a
release value of only 1 gram per inch but no greater than 30 grams
per inch. These materials are adequately non-adhesive or repellent
to reject ink from an inking roll to serve as non-image background.
Silicone resins, on the other hand, have release values in the
range of 250-550 grams per inch and are unsatisfactory as ink
repellent materials. For this purpose of this invention, a
repellent material should have a release value of 30 or less.
Materials with release values up to about 100 grams per inch have
some utility and those having a value in excess of 100 definitely
unsatisfactory for even the poorest equality of duplicator
copy.
The base, or base sheet, may be of any suitable material such as
paper, plastic, metal sheet or foil, with the properties such as
strength, flexibility, etc., being determined according to the use
to which the ultimate plate is to be put. Where an
electrophotographic base is specified, means one capable of being
electrostatically charged by a corona discharge or other
electrostatic charging means, this refers to a paper base or other
type of base coated with zinc oxide or other materials known in the
art as being capable of accepting and retaining an electrostatic
charge. These are well known in the art and numerous types are
available commercially.
Typical base materials capable of being electrostatically charged
are described in U.S. Pat. Nos. 3,052,539, 3,052,540, 3,121,006,
3,128,204, 3,160,503 and 3,481,734. In addition to zinc oxide as
photoconductive materials there may be used oxides and sulfoxides
of cadmium, mercury, antimony, bismuth, thallium, molybdenum,
aluminum, lead or zinc, as well as organic substances such as
anthracene, benzidine, anthraquinone, acenaphthene, fluoranthene,
naphthalene, etc. The resinous binding agent may be a
heat-hardenable melamine-formaldehyde resin in an amount between
0.3 and 2 parts of resin per part of zinc oxide, urea-formaldehyde
resins, xylene-formaldehyde resins, polyvinyl chloride,
polyvinylidene chloride, polyvinyl ethers, polyacrylic esters,
polymethacrylic esters, etc.
Since the invention does not reside in the particular composition
of the coating used for accepting and retaining the electrostatic
charge, and the various types available commercially are suited for
present purposes, a description of the composition of these
electrostatic bases is not considered necessary for an
understanding and practice of the present invention. In any case,
since zinc oxide coated paper is easily available, economical and
very satisfactory for this purpose, it is preferred.
Toners generally suitable for use in the commercially available
electrostatic "copying" machines are suitable for the purpose of
this invention. These are generally pigments such as carbon black,
aniline black, Prussian blue, phthalocyanine blue, red oxide,
cadmium yellow, and various resin dyes such as nigrosine resin dye,
etc., mixed with or coated with a binder material, generally a
resin or an organic material which hardens, or fuses, and thereby
binds the pigment to the base, such as zinc oxide coated paper, and
the like, on which the copy image is being made. Typical toners are
described in U.S. Pat. Nos. 3,320,169 and 3,554,946, although
various others known in the art are also suitable for this
purpose.
Various resins can be used as the binder material including such
thermoplastic and thermosetting resins as polyamides, of both the
nylon and aminoacid or polycaprolactam types, polystyrene,
polyvinylchloride, vinyl chloride-vinyl acetate copolymers,
ethylene-vinyl acetate copolymers, alkyd resins such as
pentaerythrityl abietate, etc. These resins advantageously have a
melting or curing temperature in the range of
80.degree.-150.degree. C., preferably 100.degree.-130.degree.
C.
In applying an electrostatic charge where indicated in the practice
of this invention, various types of corona discharge equipment as
are present in commercial copy units are suitable for this purpose.
In these commercial units a corona discharge is used to apply an
electrostatic charge. Depending on the particular type of equipment
used and the voltage and other conditions applying, the base
material such as the zinc oxide coated paper may be given a single
pass to develop the desired amount of electrostatic charge. In
other cases, depending on the particular conditions, several passes
may be desired for this purpose. In the example described
hereinafter, a corona discharge is used with 7,000 volts and a
metal ground plate beneath the paper. Two or three passes may be
used to develop the desired charge. However, the paticular manner
of applying an electrostatic charge is not a part of or critical to
this invention.
Various methods of practicing the invention are illustrated by the
following examples. These examples are intended merely to
illustrate the invention and not in any sense to limit the manner
in which the invention can be practiced. The parts and percentages
recited therein and all through the specification, unless
specifically provided otherwise, are by weight.
EXAMPLE I
The repellent coating is applied by preparing a solution of 20
parts of the higher molecular weight linear polydimethylsiloxane
available commercially as "G.E. RTV-108" in 80 parts heptane, the
gum being stirred into solution at room temperature. A coating is
applied by passing a commercial zinc oxide coated paper (a ZnO
resin binder coating having 70 percent ZnO and 30 percent
pentaerythrityl abietate resin binder) with the zinc oxide coated
side outward around a back-up roller positioned below a gravity
feed extrusion coating head at a web speed of about 7 feet per
minute, and applying a coating weight of polysiloxane on a dry
basis of 300 mg/sq.ft. The coating is then cured by heating for 10
minutes at 95.degree. C. in an oven situated in aa room wherein the
air at 22.degree. C., is at a relative humidity in the range of 10
- 40 percent, preferably about 30 percent relative humidity. The
coating is cured and converted to a firm, tough, highly repellent
surface.
The web is then passed through a second oven at 150.degree. C. for
about 10 minutes, whereby the adhesion to the base is improved. The
coated sheet is exposed to a corona discharge for 1.75 seconds so
that the composite sheet is electrostatically charged. The image is
superimposed on the electrostatically charged, highly ink repellent
surface and exposed to actinic light for 0.5 seconds. The light
transmitted through the non-image areas dissipates the charge in
those areas, and the charge is retained in the unexposed image
areas. Then the image is removed and a toner powder is applied to
the outer surface of the plate. This toner comprises 35 percent of
a nylon type polyamide having a melting point of about 110.degree.
C., 10 percent of a copolymer of 72 percent ethylene and 28 percent
vinyl acetate having a melting point of 255.degree. C., 45 percent
of a polystyrene having an average number molecular weight of
22,000 and a melting point of about 170.degree. C., and 10 percent
Nigrosine resin dye. The toner is not attracted by the exposed or
non-image areas on the silicone surface, but is retained in the
non-exposed or image areas, the toner being attracted and retained
by the electrostatic charge. The toner is fused, preferably by
exposure to radiant energy, in accordance with standard
procedures.
The resultant plate is run on a standard offset lithographic press
from which the water dampening system has been removed. The ink
used is a Driographic black ink (3M Driographic Ink Code 33-A).
1,000 impressions are made without any image breakdown, and the
background remains clean throughout the entire run.
EXAMPLE II
The procedure of Example I is repeated except that the
electophotographic base is omitted and a plain sheet of paper is
substituted in order to test whether exposure of the ink repellent
sheet to the corona discharge produces sufficient adhesion in the
image areas to retain ink thereon. In this case, in the absence of
the electrophotographic sheet, the ink retention is completely
unsatisfactory and in fact the surface is repellent to the ink.
EXAMPLE III
The procedure of Example I is repeated except the ink repellent
master is made by using a plain paper base and coating it with the
same organopolysiloxane. Then instead of having the image
superimposed on the ink repellent layer, it is imposed on a
separate electrostatic master charged by a corona discharge as in
Example I. The image is superimposed on this separate master and
light exposed to dissipate the charge in the exposed or non-image
areas. Toner powder is applied to this separate master as in
Example I and the image reproduced thereon. Then prior to fusing
the toner image from the separate master is superimposed on the
organopolysiloxane surface of the coated paper and applied by hand
pressure so that the toner image is transferred from the separate
master to the surface of the ink repellent siloxane layer. The
coated paper having the toner imprint thereon is then fused in
accordance with the procedure of Example I. The resultant plate is
used in running off 2,000 copies of positive prints to give good,
clear images with the background remaining clear throughout the
entire run. This procedure may be repeated using various materials
such as aluminum sheet, plastic sheet, etc., in place of the paper.
In each case a plate is made which gives good, clear images when
used for printing as in Example I.
EXAMPLE IV
The procedure of Example III is repeated using in place of the
plain paper base the same electrostaticallly chargeable paper as
used in Example I and an electrostatic charge is applied to this as
in Example I prior to the transfer of the toner image as in Example
III. The resultant plate gives equivalent printing results as
compared with Example III.
EXAMPLE V
The procedure of Example I is repeated using in place of the toner
of that example a toner having the composition: 50 percent of a
pentaerythrityl abietate resin; 35 percent of a polyamide resin
similar to that used in Example I: 5 percent stearic acid; 5
percent carbon black and 5 percent Nigrosine resin dye. Excellent
printing results are obtained.
EXAMPLE VI
The procedure of Example I is repeated using in place of the toner
of that example a toner having the composition: 25 percent of the
polyamide used in Example I; 21 percent of a maleic anhydride resin
condensation product; 24 percent stearamide; 16 percent of butyl
laurate; and 14 percent of Nigrosine resin dye. Again excellent
printing results are obtained.
EXAMPLE VII
The procedure of Example I is repeated a number of times using
mixtures of zinc oxide and the polysiloxane as the coating
material. Mixtures containing 50 percent, 40 percent and 25 percent
by weight of zinc oxide are used individually to give excellent
printing results in each case.
While certain features of this invention have been described in
detail with respect to various embodiments thereof, it will, of
course, be apparent that other modifications can be made within the
spirit and scope of this invention and it is not intended to limit
the invention to the exact details shown above except insofar as
they are defined in the following claims.
* * * * *