U.S. patent number 3,617,266 [Application Number 04/710,723] was granted by the patent office on 1971-11-02 for process for preparing a planographic printing form.
This patent grant is currently assigned to Gevaert-Agfa N.V.. Invention is credited to Noel Jozef De Volder, Jozef Leonard Van Engeland, Jozef Frans Williams.
United States Patent |
3,617,266 |
Williams , et al. |
November 2, 1971 |
PROCESS FOR PREPARING A PLANOGRAPHIC PRINTING FORM
Abstract
A planographic printing plate prepared by electrostatic exposure
and development and carrying a hydrophobic deposit from such
development in the image areas thereof is hydrophilized by
treatment with an aqueous solution containing a polymeric compound
having in the recurring units thereof an amino salt and/or
quaternary salt group the polymer compound being free of long chain
hydrocarbon groups. Preferred hydrophilizing compounds are
polyamines having aliphatic linkages between the amino groups and
polyvinyl compounds having hydrogen-containing heterocyclic side
groups.
Inventors: |
Williams; Jozef Frans (Wilrijk,
BE), Van Engeland; Jozef Leonard (St.
Katelijne-Waver, BE), De Volder; Noel Jozef (Edegem,
BE) |
Assignee: |
Gevaert-Agfa N.V. (Mortsel,
BE)
|
Family
ID: |
27256529 |
Appl.
No.: |
04/710,723 |
Filed: |
March 6, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Mar 6, 1967 [GB] |
|
|
10476/67 |
|
Current U.S.
Class: |
430/49.7;
101/451; 101/465 |
Current CPC
Class: |
G03G
13/28 (20130101) |
Current International
Class: |
G03G
13/28 (20060101); G03g 013/22 (); G03f
007/02 () |
Field of
Search: |
;96/1,33 ;101/451,465
;117/62,17.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Van Horn; Charles E.
Claims
What we claim is:
1. In a process for preparing a planographic printing plate
comprising the steps of forming a latent electrostatic image on a
photoconductive insulating recording layer containing an inorganic
photoconductive substance, which can provide zinc ions, and
developing said image with a toner forming an image-wise
hydrophobic deposit on said recording layer, the improvement of
treating the portions of the recording layer which are not covered
with said hydrophobic deposit with an aqueous hydrophilizing
solution containing a a water-soluble polyamino compound comprising
at least two nonaromatic amino groups with each adjacent pair of
such amino groups being connected by an aliphatic linkage including
a hydrocarbon chain of at least two but not more than six carbon
atoms, said compounds containing not more than six carbon atoms in
a continuous carbon chain, at least part of the amino groups in
said compound being in amine salt or quaternized salt form.
2. Process for preparing a planographic printing plate according to
claim 1, wherein the polymeric compound is applied in the aqueous
liquid of a damping system of a planographic printing device.
3. Process for preparing a planographic printing plate according to
claim 1, wherein the polymeric compound is applied in the aqueous
phase of a planographic printing ink composed of a lipophilic phase
dispersed in a hydrophilic phase.
4. Process for preparing a planographic printing plate according to
claim 1, wherein the polymeric compound is used in dissolved form
in an aqueous liquid in a concentration of 0.01 to 20 percent by
weight calculated on the total weight of the liquid.
5. Process for preparing a planographic printing plate according to
claim 1, wherein polymeric compound is used in an aqueous liquid
having a pH lower than 7.
6. Process for preparing a planographic printing plate according to
claim 1, wherein the polymeric compound is used in combination with
ferricyanide and/or ferrocyanide ions.
7. Process for preparing a planographic printing plate according to
claim 1, wherein the polymeric compound is used in combination with
a hydrophilic colloid.
8. ##SPC3##
9. Process for preparing a planographic printing plate according to
claim 10, wherein the polyamine compound is polyalkylene-polyimine
compound having at least part of the amino groups thereof
transformed into a salt form or a quaternized form.
Description
This invention relates to a process for preparing planographic
printing plate and to the printing plate obtained therewith.
Planographic printing is based on the physical property of
repellence of greasy materials for water. The printing surface,
which is substantially flat, contains the pattern of the image to
be printed in terms of a differentiation in water repellency. In
the ordinary lithographic or planographic printing processes a
printing plate is prepared by affixing to a water-attractive,
hydrophilic surface, a water repellent, hydrophobic image, usually
greasy, resinous or waxy in nature.
There are several methods known for preparing a lithographic
printing plate. According to one of them use is made of a
photoconductive insulating material such as an electrophotographic
recording layer containing photoconductive zinc oxide dispersed in
an electrically insulating binder. To prepare the printing surface
said layer is electrostatically charged and image-wise exposed.
The electrostatic image according to the electrical sign of the
electrostatically attractable developer particles in respect of the
applied charge may be developed as a negative or a positive of the
original to be reproduced. According to a common technique the
electrostatic image is rendered visible by applying a developer
powder, which is held electrostatically to the charged areas of the
sheet. The powder image preferably composed of hydrophobic fusible
powder particles may be fixed by heating. Normally the difference
in hydrophobicity between the developed image parts and the
noncovered areas of the recording layer is not high enough for high
quality planographic printing and has to be increased. Therefor it
has been proposed to treat the recording layer chemically in the
undeveloped areas in order to make said areas highly
water-receptive.
It has been found now that a photoconductive insulating recording
layer comprising an electrically insulating binder having suspended
therein an inorganic photoconductive substance that can provide
zinc ions, such as photoconductive zinc oxide, can be provided with
improved hydrophility by treating it with a polyamino compound
comprising at least two nonaromatic amino groups, e.g. aliphatic,
cycloaliphatic, cyclo- or heterocyclic amino groups without
aromatic character, at least one of these amino groups being
present in salt form or quaternized form.
The aliphatic or cycloaliphatic chains of the nonaromatic amine
groups may consist entirely of chains of carbon atoms, or the
chains may contain carbon atoms interspaced with oxygen, sulfur
nitrogen or phosphorus atoms or combinations thereof. Thus the
chains may contain ester, amide, ether, imidazole, or urethane
linkages, or their thio-equivalents.
Use is preferably made of a polymeric compound containing one or
more aliphatic amino groups in the recurring units e.g. a
polyalkyleneimine compound wherein part of the amino groups or all
of them are transformed into a salt form or a quaternized form.
Particular representatives of such polyamino compounds are listed
in the following table.
TABLE
1. h.sub.2 n-(ch.sub.2 -ch.sub.2 -nh).sub.n -CH.sub.2 -CH.sub.2
-NH.sub.2 (acid neutralized) wherein:
n is an integer from 2 to 50.
wherein:
R is a C.sub.1 -C.sub.5 alkyl group;
x is an integer from 2 to 50, and
compounds of this type are sold under the trade name
Solidogen by Cassella Farbwerke Mainkur A.G. Frankfurt
(Main). A preferred product is "SOLIDOGEN FFL."
wherein:
m is an integer from 2 to 50.
(partly quaternized polyethyleneimine).
wherein:
X.sup.- is an anion, e.g. a chloride ion and
n is an integer from 2 to 50. ##SPC1## ##SPC2##
Poly(N-Vinyl-2-methylimidazolium methylsulphate) sold under the
trade name ANTI-STATIN LF by Badische Anilin- & Soda-Fabrik
A.G. Ludwigshafen, West Germany.
Further polymeric amino compounds suitable for use according to the
present invention are described in the published Dutch Pat.
applications Nos. 6,614,230, 6,614,291 and 6,711,152.
The polyamino compounds for use according to the present invention
are preferably dissolved in an aqueous liquid in a concentration of
0.1 to 20 percent by weight calculated on the total weight of the
liquid.
The polyamino compounds comprising amino group(s) in neutralized or
quaternized form are preferably used in combination with
water-soluble ferricyanides and/or water-soluble ferrocyanides
since the sparingly water-soluble hydrophilic zinc salts formed
therewith have a relatively high adsorption power for cationic
compounds and therefore have a mordanting effect on said
neutralized or quaternized polyamino compounds.
A printing plate containing in the hydrophilized portions a
coprecipitate of zinc ferri- and/or zinc ferrocyanide and a
neutralized or quaternized polyamine has a high resistance to wear,
which is important for long run printing. That resistance to wear
can still be increased with hydrophilic colloids which may be
applied simultaneously with or after the treatment with said
polyamines. Suitable hydrophilic colloids for that purpose are e.g.
gum arabic, alginic acid, water-soluble alginates e.g. ammonium
alginate, caseinates, gelatin, polyacrylic acid esters, polystyrene
sulfonic acid, polyvinyl alcohol, and carboxymethylcellulose. A
treatment with hydrophilic precipitating or hardening agents for
these colloids has proved to be advantageous. So, use can be made
of formaldehyde as protein hardener and heavy metal salts forming a
precipitate e.g. with alginates.
In order to set free zinc ions from the photoconductive layer
containing a photoconductive zinc compound, the pH of the
hydrophilizing liquid is preferably below 7 and more preferably
within the range of 3 to 6. For acidifying the developing liquid
water-soluble mineral and/or organic acids can be used e.g.
orthophosphoric acid, nitric acid, sulfuric acid, hydrochloric
acid, boric acid, acetic acid, citric acid, tartaric acid, tannic
acid and lactic acid.
The hydrophilizing action of the hydrophilizing agent may be
improved by a pretreatment of the developed and fixed recording
layer with a softening or swelling agent for the binder
occasionally in combination with a wetting agent improving the
penetrating power of the hydrophilizing agent in the recording
layer. In this way much more zinc oxide grains are reached by the
hydrophilizing agent and hydrophilized.
As swelling agents preferably water-miscible compounds such as
acetone and methyl ethyl ketone are used.
According to a preferred embodiment the electrophotographic
recording layer is rendered water-receptive at the areas to be
hydrophilized after the printing master has been mounted on the
press, thus obviating any separate immersion treatment. The
hydrophilizing treatment of said layer may be carried out by means
of an absorbent pad impregnated with an aqueous solution containing
the partly or wholly neutralized or quaternized polyamine.
Electrophotographic recording materials, which are especially
suited to be used in the preparation of a planographic printing
plate, are described e.g. in the published Dutch Pat. applications
6,608,814 and 6,608,815.
Any known process for forming the electrostatic latent image and
hydrophobic image may be applied.
According to a common technique the hydrophobic image is formed by
the consecutive steps of producing an electro-static image on a
photoconductive zinc oxide/hydrophobic binder layer by integrally
electrostatically charging that layer, subsequently image-wise
exposing and developing the latter with a hydrophobic developer
powder, which is fixed to the recording layer e.g. by heating.
The powder image can be formed by the known dry "carrier-toner
development" or by a liquid development based on electrophoresis
wherein charged hydrophobic particles are attracted from an
electrically insulating liquid to be charged areas of the recording
layer. Such development technique is described e.g. in the U.K.
Pat. specification 755,486.
According to a developing technique in the U.K. Pat. specifications
987,766, 1,010,505, 1,020,503, 1,033,419 and 1,033,420 an
electrostatic latent image can also be developed by a selective
deposit of an aqueous developing composition. That composition can
e.g. contain a dispersed hydrophobic polymer, which on drying the
liquid image is image-wise left and forms a hydrophobic
pattern.
It is self-explanatory that the polyamines applied according to the
present invention can be used in combination with other
hydrophilizing compounds.
The following examples illustrate the present invention without,
however, limiting it thereto.
EXAMPLE 1
A layer of photoconductive material consisting of photoconductive
zinc oxide dispersed in an insulating binder (3 parts by weight of
zinc oxide to 1 part by weight or resin binder) was coated on a
sheet of aluminum foil laminated to a paper support. The resin
binder contained on a weight basis 80 % of styrene-butadiene
copolymer (80/20), 20 % of silicone resin (Silicone Resin SR-82
supplied by General Electric Silicone Products Department
Waterford, N.Y., U.S.A.). The recording layer was charged with a
negative corona with a tension of - 6000 v. on the corona wires and
exposed through a graphic original. Development was carried out by
using the magnetic brush technique with iron particles as carrier
and gilsonite as fusible toner. The powder image was fixed to the
layer by heating for 90 seconds at 140.degree. C.
A cotton pad was impregnated with a solution containing the
following ingredients:
50 percent aqueous solution of a high molecular weight (15,000)
polyethyleneimine quaternized with dimethylsulphate 3 cc.
water 97 cc.
The plate was rubbed softly with the cotton pad while on the press.
The quality of prints was very good.
On using 1 percent by weight of the said hydrophilizing compound
together with phytic acid for maintaining the pH to 5 in the liquid
of the damping system of a common offset printing device up to 5000
of excellent sharp copies could be obtained.
EXAMPLE 2
Example 1 was repeated with the proviso, however, that the
hydrophilizing liquid used contained 3 percent by weight of
compound 1 (n= 3) neutralized with 3 cc. of a 1 percent aqueous
tannic acid solution. The quality of the plate was only a little
inferior to that of example 1.
EXAMPLE 3
Example 1 was repeated with the proviso, however, that the
hydrophilizing liquid used contained 3 percent by weight of
compound 3 (m= 10). The quality of the plate was equivalent to that
of example 1.
EXAMPLE 4
Example 1 was repeated, with the proviso, however, that the
hydrophilizing liquid used contained 3 percent by weight of 4
(X.sup.-= C1.sup.- and n= 30). The quality of the plate was
equivalent to that of example 1.
EXAMPLE 5
Example 1 was repeated, with the proviso, however, that the
hydrophilizing liquid used contained 6 percent by weight of
polyethyleneimine (n= 30-50). 50 percent of the -NH- groups being
quaternized with dimethyl sulfate
EXAMPLE 6
A layer of photoconductive material consisting of photoconductive
zinc oxide dispersed in an insulating binder (6 parts by weight of
zinc oxide to 1 part by weight of binder) was coated on a flexible
aluminum foil.
The binder was prepared from a mixture of EPOK X-1772 (ammoniacal
alkyd resin salt marketed as a 66 to 68 percent (by weight) aqueous
solution by British Resin Products Ltd.) and EPOK W-9801 (a 72 to
75 percent aqueous solution of a melamine-formaldehyde resin
marketed by British Resin Products). The coated layer was dried for
24 hours at room temperature and cured for 1 min. at 100.degree.
C.
The cured recording layer was charged with a negative corona with a
tension of - 6000 v. on the corona-wires and exposed to a
line-copy.
The electrostatic image was electrophoretically developed by means
of an electrophoretic developer obtained by diluting the
hereinafter described concentrated developer composition in a
volume ratio of 15/1000 with the hydrocarbon solvent SHELLSOL T
(trade name)
carbon black (average particle size 20 .mu. ) 30 g.
zinc monotridecyl phosphate 1.5 g.
Shellsol t (trade name) 750 cc.
resin solution prepared as described
hereinafter 150 g.
The resin binder solution was prepared by heating 500 g. of ALKYDAL
L 67 [ trade name by Farbenfabriken Bayer AG, Leverkusen, West
Germany, for a linseed oil (67 percent by weight) modified alkyd
resin] and 500 cc. of white spirit containing 11 percent by weight
of aromatic compounds at 60.degree. C. till a clear solution was
obtained, and subsequent cooling.
Hydrophilization of the developed plate was effected by softly
rubbing with a cotton pad soaked in an aqueous solution containing
the following ingredients:
Solidogen ffl (trade name) 5 cc.
sodium ferrocyanide 1 g.
sodium sulfite (antioxidant) 2.5 g.
water 100 cc.
The quality of the plate was better in respect of wear than that of
the plate obtained in example 1.
EXAMPLE 7
Example 6 was repeated, with the proviso, however, that the
hydrophilizing liquid was acidified till pH 3 by means of tartaric
acid, phosphoric acid, citric acid, phytic acid, or oxalic
acid.
Hydrophilization was more effective than was the case according to
the procedure of example 6.
EXAMPLE 8
Example 1 was repeated, with the proviso, however, that the
hydrophilizing liquid used contained 5 percent by weight of the
compound 14. The plate quality was practically the same as that
obtained according to the procedure of example 1.
EXAMPLE 8-11
Example 1 was repeated with the proviso, however, that the
hydrophilizing liquid was acidified till pH 6 and that it contained
5 percent by weight of the quaternized polyamino compound No. 6 of
the table. The hydrophilization obtained was equivalent to that
according to the procedure of example 1. Results of slightly
inferior quality were obtained by using the compounds Nos. 7, 8 and
9 in the same concentration at pH values of 6, 2 and 6
respectively.
EXAMPLES 12-15
Example 1 was repeated with the proviso, however, that aqueous
hydrophilizing liquid was acidified with hydrochloric acid till pH
2 and that it contained in a concentration of 5 percent by weight
the compounds Nos. 10, 11, 12 or 13 respectively.
* * * * *