FIELD OF THE INVENTION
[0001] The present invention relates to a plate cleaner for a lithographic printing plate
which is made by an electrophotographic process.
BACKGROUND OF THE INVENTION
[0002] If an electrophotographic process is employed for making a lithographic printing
plate, the printing plate can be easily made through only simple procedures of forming
an image according to ordinary electrophotographic steps, and then wiping the copied
surface of an electrophotographic photoreceptor with such a desensitizing solution
(also called etching solution) as to render the non-image area hydrophilic, that is
to say, only procedures requiring no special techniques.
[0003] For instance, photoconductive zinc oxide is coated together with a binder on a base
paper which has previously been so treated as to have a water resisting property.
The thus-formed photoconductive layer is subjected to corona discharge or the like
to gain charges electrostatically. Then, it is exposed to a light pattern in the dark,
whereby charges in the exposed areas are dissipated and those in the non-exposed areas
remain. Thus, electrostatic latent image is created on the photoconductive layer.
The latent image is developed by then spraying charged toner particles onto the photoconductive
layer or dipping the photoconductive layer in an insulating liquid in which charged
particles are dispersed, thereby causing the charged toner particles to adhere thereto
by Coulombic attraction in an imagewise pattern.
[0004] In general, toner particles used in a developer are coated with an oleophilic resin,
and fixed to a photoconductive layer by a process of heat sealable adhesion or evaporation
of solvent.
[0005] Thus, the image part displays an oleophilic property due to the oleophilic resin
coat of toner particles. In order to convert an electrophotographic copy obtained
thereby to a lithographic printing plate, it is necessary for the non-image part to
be rendered hydrophilic. Such can be done, for example, in the following manner. When
the copied face is wetted with a desensitizing solution which can convert certain
substances into those having a strong affinity for water, e.g., a solution in which
potassium ferrocyanide, potassium ferricyanide, ammonium phosphate or so on is dissolved,
it is observed that a film of a water- insoluble precipitate (e.g., K
2Zn
3[Fe(CN)
6]
2' ZnNH
4PO
4, etc.) is formed in the part to be rendered hydrophilic by the reaction of the above-described
solute with zinc oxide which constitutes the photoconductive layer. The operation
is very simple, since it suffices for the wetting procedure to simply wipe the copied
face with absorbent cotton or gauze dampened with a solution as above described.
[0006] Preferred desensitizing solutions are explained in detail in U.S. Patents 3,001,871,
3,592,640 and 4,208,212.
[0007] When printing from a lithographic printing plate obtained by the above-described
procedure, the hydrophilic property of the non-image part tends to deteriorate for
one reason or another. Ink often sticks to such areas, causing so-called background
contamination. A typical cause of background contamination, though the contamination
is attributed to a wide variety of causes, involves the drying of the plate surface
after treatment for rendering hydrophilic. When the plate surface is dried, it happens
that ink adheres to the dried areas in spots or over the whole plate surface at the
time of printing. A phenomenon like this can be also observed when a printing machine
is stopped in the course of printing on account of machine trouble or for the purpose
of taking a rest. Another cause involves adhesion of oleophilic substances to an uncovered
hydrophilic layer. In this case, the adhesion spots become ink-receptive, and are
turned into stains. Also, it can be attributed to a similar cause, viz., fingerprints,
which have been left on the hydrophilic layer before treatment for rendering the non-image
part of the photoconductive layer hydrophilic, make their appearance at the background
of printed matter.
[0008] Hitherto, in the case of a typical PS plate (which is the abbreviation of Pre-Sensitized
printing plate, that is to say, a lithographic printing plate to which photosensitivity
is imparted in advance) the stains can be removed by wiping with dampening water or
an etching solution and thereby the plate surface can be restored to the original
state to some degree. On the other hand, an electrophoto-lithographic printing plate
has a strong affinity for printing ink, and therefore the stains can hardly be changed
for the better by wiping with an etching solution or a washing oil. In addition, although
various kinds of plate cleaner have been provided for PS plates, application of such
cleaner to electrophoto-lithographic printing plates cannot reduce the background
contamination due to their insufficient effect upon removal of the printing ink, and,
what is worse, it happens that the photoreceptive layer of an electrophoto-lithographic
printing plate is destroyed by application of such cleaner to rather generate stains.
Such being the case, cleaners fit for practical use have not yet been presented, and
the advent of a plate cleaner specifically for use with an electrophoto-lithographic
printing plate's exclusive use has been ardently desired.
SUMMARY OF THE INVENTION
[0009] Therefore, a primary object of the present invention is to provide a plate cleaner
for an electrophoto-lithographic printing plate which can restore the plate surface
from stains generated in the course of printing operations, stains due to fingerprints
or ink left on the plate surface before or after the treatment for rendering the non-image
part of the photoconductive layer hydrophilic, or stains caused by scratches, and
enables normal printing which is free from background contamination.
[0010] As a result of extensive investigations, it has now been found that the above-described
object can be attained by using as a plate cleaner a suspension or an emulsion comprising
as main components:
(1) an aqueous solution of a compound capable of producing a hydrophilic substance
by reaction with zinc oxide,
(2) a hydrocarbon solvent having an action of dissolving lithographic printing ink,
and
(3) a surface active agent.
[0011] In addition to the above-described principal components, the cleaner of the present
invention may preferably additionally comprise the following components:
(4) a water-soluble collidal substance,
(5) a wetting agent, and
(6) at least one compound selected from the group consisting of molybdic acid, boric
acid, nitric acid, phosphoric acid, polyphosphoric acid, and water-soluble alkali
metal salts thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0012] Examples of compounds capable of producing hydrophilic substances by reacting with
zinc oxide, which are employed as the component (1) in the present invention include
ferrocyanide compounds such as potassium ferrocyanide, sodium ferrocyanide, etc.;
ferricyanide compounds such as potassium ferricyanide, sodium ferricyanide, etc.;
phosphoric acid compounds such as ammonium primary phosphate, ammonium secondary phosphate,
etc.; phytic acid and the derivatives thereof, that is, phytic acid compounds, as
described in Japanese Patent Application (OPI) No. 127002/78 (the term "OPI" as used
herein refers to a "published unexamined Japanese patent application"); polyvalent
metal salts such as ferric chloride, cupric chloride, etc.; hexamminecobalt salts,
hexamminenickel salts, EDTA (ethylenediaminetetraacetate) chelate compounds, and the
like, as described in U.S. Patent 4,282,811; polyacrylic acid, sodium polyacrylate,
polymethacrylic acid, sodium polymethacrylate, alginic acid, sodium alginate, cationic
polymers such as melamine- formaldehyde resin, and so on. Compounds to be employed
as the component (1) are not limited to any particular compounds, provided that they
can react with zinc oxide to produce hydrophilic substances. Further, they can be
used as a mixture of two or more thereof. It is preferred in the present invention
to use these compounds in a condition of water solution. The water solution is preferably
adjusted to a pH of from 2 to 6. It is advisable to use the above-described compounds
in combination with an acid or a base such as ammonia, phosphoric acid, ammonium phosphate,
citric acid, sodium citrate, or the like.
[0013] The hydrocarbon solvent of the component (2) employed in the present invention is
one which has an action of dissolving lithographic printing ink, and an especially
useful hydrocarbon solvent is a petroleum fraction ranging in boiling point from 120°C
to 320°C, which is conventionally used in washing for removal of ink. This hydrocarbon
solvent is generally used in an amount corresponding to from 5 to 50%, and preferably
from 10 to 40%, of the total weight of the cleaner composition.
[0014] As the component (1) and the component (2) are immiscible, they are thoroughly mingled
and dispersed and put to use in such a dispersed condition.
[0015] Preferred surface active agents forming the component (3) employed in the present
invention are those having anionic or nonionic character, and have the function of
enhancing dispersibility of the system. Examples of preferred anionic surface active
agents include aliphatic salts, higher alcohol sulfate salts, aliphatic alcohol phosphate
salts, sulfonic acid salts of dibasic fatty acid esters, fatty acid amide sulfonic
acid salts, alkylarylsulfonic acid salts, and formaldehyde-condensed naphthalenesulfonic
acid salts.
[0016] Examples of preferred nonionic surface active agents which can be used include polyoxyethylene
alkyl ethers, polyoxyethylene alkylphenol ethers, polyox
y- ethylene alkyl esters, sorbitan alkyl esters, polyox
y- propylene, polyoxyethylene ethers and so on. These surface active agents may be used
in combinations of two or more thereof. The quantity of such surface active agents
used in the cleaner is, though not particularly limited, preferably in the range of
not more than 10% of the total weight of the cleaner composition.
[0017] Besides adding the surface active agent of the component (3), it is preferable in
the present invention to add a water-soluble colloidal substance as a component (4)
for the purpose of further enhancing the dispersing stability of the cleaner.
[0018] Specific examples of preferred water-soluble colloidal substances which can be preferably
used in the present invention include natural resins or modified resins thereof such
as dextrin, gum arabic, shellac, alginic acid salts, cellulose deriva-tives (e.g.,
carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, methyl cellulose,
etc.), and so on; and synthetic resins such as polyvinyl alcohol and the derivatives
thereof, polyvinyl pyrrolidone, polyacrylamide and copolymers thereof, acrylic acid
copolymers, vinyl methyl ether/maleic anhydride copolymers, vinyl acetate maleic anhydride
copolymers, styrene/maleic anhydride copolymers, and so on. These substances can be
used alone or as a mixture.
[0019] In addition to the above-described components, one or more wetting agents are also
useful as a component (5) in the plate cleaner for the purpose of imparting an excellent
spread characteristic and retarding the progress of drying and thereby making an improvement
in using facility. Suitable wetting agents are compounds of the formula HO(̵R-O)̵
mH [wherein R is C
nH
2n (n is an integer from 2 to 6) and m is from 1 to 500]. Of such compounds, ethylene
glycol, propylene glycol, butylene glycol, pentanediol, hexylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene
glycol, tripropylene glycol, and the like are preferably used. Other wetting agents
which can be used advantageously are glycerin, sorbitol, and pentaerythritol.
[0020] The characteristics of the plate cleaner of the present invention are that they can
exert a very strong action preventing background contamination due t6 scratches the
hydrophilic layer received, and perform a powerful function in maintaining or reinforcing
the recovered hydrophilic property. Said characteristics are further intensified by
using as the component (6) at least one compound selected from the group consisting
of molybdic acid, boric acid, nitric acid, phosphoric acid or polyphosphoric acid,
and water-soluble alkali metal salts thereof together with the foregoing components.
Such a compound as described above is typically used in a range of from 0.1 to 10%,
and preferably from 0.2 to 5%, of the total weight of the cleaner composition.
[0021] The plate cleaner of the present invention may also contain in itsm composition granular
powders such as pumice, alumina powder, silica powder and the like, colloidal silica,
colloidal alumina, dyes and so on in addition to the above-described ingredients.
[0022] The present invention will now be illustrated in greater detail by reference to the
following examples. However, the invention is not intended to be construed as being
limited to these examples. Unless otherwise indicated, all parts and all percents
are by weight.
EXAMPLE 1
[0023] In 70 parts of distilled water were dissolved 10 parts of glycerine, 10 parts of
ammonium primary phosphate, 5 parts of potassium ferrocyanide, 2 parts of gum arabic
and 3 parts of polyethylene glycol oleyl ether (Noigen ET-120, produced by Dai-ichi
Kogyo Seiyaku Co., Ltd.), and the resulting solution was named Solution A.
[0024] Separately, 4 parts of sorbitol oleic acid monoester (Nissan Nonion OP-80, produced
by Nippon Oils & Fats Co., Ltd.) was dissolved in 20 parts of n-heptane, and named
Solution B.
[0025] Then, Solution B was slowly added dropwise to Solution A with stirring, and dispersed
into Solution A. The resulting dispersion was made into a yellow emulsion by means
of a homogenizer.
[0026] A lithographic printing plate was prepared by means of a commercially available offset
master-making machine, ELP-280 (made by
Fuji Photo Film Co., Ltd.). The electrophotographic light-sensitive material used in
the production of the printing plate was produced by coating the following composition
on a waterproof paper rendered electroconductive to obtain a photoconductive layer
having a dry thickness of 10 µ.

[0027] The developer used hereinabove had the following formulation.

[0028] After fingerprints were formed on a non-image area of the printing plate thus prepared,
a desensitizing solution having the following composition was applied to the whole
surface of the printing plate.
Desensitizing Solution:
[0029]

[0030] Then, the printing test was carried out using a printing machine Hamadastar 700 CD.
As a result, generation of stains was observed on the part where fingerprints had
been put. After 100 sheets of copies had been printed, the operation of the printing
machine was suspended, and the finger marks (to which ink had already adhered) was
wiped with the plate cleaner prepared herein and thereafter the printing machine was
operated again. Thus, not less than 10,000 copies which had good quality and no finger
marks were obtained. Of course, these copies showed no abnormality in the image part
and others.
EXAMPLE 2
[0031] Both Solutions 2A and 2B having the following formulae respectively were prepared
in the same manner as described in Example 1, and another plate cleaner was obtained.

[0032] A lithographic printing plate was made in the same manner as employed in Example
1 and finger marks were formed thereon with ink-stained fingers, followed by subjecting
it to the same treatment for acquiring hydrophilic property with the desensitizing
solution used in Example 1. Printing was carried out using the resulting printing
plate, and stains of a fingerprint pattern were observed in the printed matter. After
100 copies had been printed, the operation of the printing machine was suspended,
and the finger marks (to which ink had already been sticked) were wiped with the above-described
plate cleaner, and thereafter the printing machine was operated again. Thus, not less
than 10,000 copies which had good quality and no finger marks were obtained. Furthermore,
these copies showed no abnormality in the image part, e.g., no deterioration in inking.
EXAMPLE 3
[0033] Both solutions 3A and 3B having the following formulae respectively were prepared
in the same manner as employed in Example 1, and still another plate cleaner was obtained.

[0034] A lithographic printing plate made in the same manner as employed in Example 1 was
placed in a printing machine, Hamadastar 700 CD, and ink was put on a part of the
plate surface using an inking roller. Then, the resulting plate was rendered hydrophilic
using the etching solution used in Example 1. As a result of printing, intense printing
stain was generated in the part where the inking had been carried out before the treatment
for rendering hydrophilic. The operation of the printing machine was suspended, and
the plate surface was wiped with the above-described cleaner. Thereafter, the operation
was started again, and more than 10,000 copies which had good quality and no stain
were obtained. Furthermore, these copies showed no abnormality in the image part.
EXAMPLE 4
[0035] A lithographic printing plate made in the same manner as employed in Example 1 was
treated as to acquire an affinity for water, and printing was carried out using the
resulting printing plate. Then, the printing operation was suspended, and the plate
surface got scratches by being rubbed with sandpaper. Thereafter, the printing machine
was operated again. As a result, the scratching marks remained as stains on the prints.
Therefore, the printing operation was suspended again, and the plate surface was wiped
with the plate cleaner prepared in Example 1. Thereafter, more than 10,000 copies
having good quality and no scratch stain were obtained. In addition, it was recognized
similarly that the plate cleaner prepared in Example 2 and Example 3, respectively,
had an improving effect (i.e., minimized) on scratch stain.
[0036] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.
1. A plate cleaner for an electrophoto- lithographic printing plate which comprises
a suspension or an emulsion containing as main components (1) a water solution of
a compound which can produce a hydrophilic substance by reaction with zinc oxide,
(2) a hydrocarbon solvent, and (3) a surface active agent.
2. A plate cleaner as in claim 1, wherein said compound of component (1) is selected
from the group consisting of ferrocyanide compounds, ferricyanide compounds, phosphoric
acid compounds, phytic acid compounds, polyvalent metal salts, hexamminecobalt salts,
hexamminenickel salts, EDTA chelate compounds, poly-acrylic acid, sodium polyacrylate,
polymethacrylic acid, sodium polymethacrylate, alginic acid, sodium alginate and cationic
polymers.
3. A plate cleaner as in claim 1, wherein said surface active agent is an anionic
or a nonionic surface active agent.
4. A plate cleaner as in claim 1; wherein said hydrocarbon solvent is petroleum fraction
ranging in boiling point from 120°C to 320°C.
5. A plate cleaner as in claim 4, wherein said hydrocarbon solvent is contained therein
in range of from 5 to 50 wt% of the total weight of the composition.
6. A plate cleaner as in claim 2, wherein said surface active agent is an anionic
or nonionic surface active agent, and said hydrocarbon solvent is a petroleum fraction
ranging in boiling point from 120°C to 320°C.
7. A plate cleaner as in claim 6, wherein said hydrocarbon solvent is contained therein
in a range of from 5 to 50'wt% of the total weight of the composition.
8. A plate cleaner as in claim 1, wherein said cleaner additionally comprises as component
(4) a water-soluble colloidal substance.
9. A plate cleaner as in claim 6, wherein said cleaner additionally comprises as component
(4) a water-soluble colloidal substance.
10. A plate cleaner as in claim 1, additionally comprising a wetting agent component.
11. A plate cleaner as in claim 6, additionally comprising a wetting agent component.
12. A plate cleaner as in claim 1, additionally comprising a compound selected from
the group consisting of molybdic acid, boric acid, nitric acid, phosphoric acid, polyphosphoric
acid, and water-soluble alkali metal salts thereof.
13. A plate cleaner as in claim 6, additionally comprising a compound selected from
the group consisting of molybdic acid, boric acid, nitric acid, phosphoric acid, polyphosphoric
acid, and water-soluble alkali metal salts thereof.
14. A plate cleaner as in claim 8, additionally comprising as component (5) a wetting
agent.
15. A plate cleaner as in claim 9, additionally comprising as component (5) a wetting
agent.
16. A plate cleaner as in claim 14, additionally comprising as component (6) a compound
selected from the group consisting of molybdic acid, boric acid, nitric acid, phosphoric
acid, polyphosphoric acid, and water-soluble alkali metal salts thereof.
17. A plate cleaner as in claim 15, additionally comprising as component (6) a compound
selected from the group consisting of molybdic acid, boric acid, nitric acid, phosphoric
acid, polyphosphoric acid, and water-soluble alkali metal salts thereof.
18. A plate cleaner as in claim 14, wherein the water-soluble colloidal substance
component (4) is at least one of a natural resin selected from the group consisting
of dextrin, gum arabic, shellac, alginic acid salts, cellulose derivatives, and a
synthetic resin selected from the group consisting of modified natural resins, polyvinyl
alcohol and derivatives thereof, polyvinyl pyrrolidone, polyacrylamide and copolymers
thereof, acrylic acid copolymers, vinyl methyl ether/ maleic anhydride copolymers,
vinyl acetate/maleic anhydride copolymers, and styrene/maleic anhydride copolymers.
19. A plate cleaner as in claim 14, wherein said wetting agent component (5) is selected
from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentanediol,
hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene
glycol, dipropylene glycol, and tripropylene glycol.
20. A process for preventing background stains of a lithographic plate, comprising
treating the lithographic plate surface which is produced by an electrophotographic
process from an electrophotographic plate containing ZnO photoreceptor, with the plate
cleaner defined in claim 1.