|Publication number||US2983220 A|
|Publication date||May 9, 1961|
|Filing date||Mar 16, 1955|
|Priority date||Mar 16, 1955|
|Publication number||US 2983220 A, US 2983220A, US-A-2983220, US2983220 A, US2983220A|
|Inventors||Dalton Harold R, Murray Wolf|
|Original Assignee||Timefax Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (11), Referenced by (22), Classifications (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
May 9, 1961 H. R. DALTON ErAL 2,983,220
ELECTRO-SENSITIVE PLANOGRAPHIC PRINTING PLATE Filed March 1e. 1955 1N V EN TORS. HAROLD IQ. @ALTO/V MU/QQA V WOLF DI? EK United States Patent ELECTRO-SENSITIVE PLANOGRAPHIC PRINTING PLATE Filed Mar. 16, 1955, Ser. No. 494,683
7 Claims. (Cl. lOl-149.2)
This invention relates to exible base electro-responsive planographic printing plates and to the methods of manufacture and compositions of such planographic plates.
A principal object of the'inyention is to provide an electro-responsive recording blank which may have an image of subject matter produced thereon in response to the action of electric currents or potentials applied thereto, such for example as telefacsimile signals and the like, and which imaged blank may subsequently be used as a planographic printing plate on a planographic printing press.
In the art ofl imaging cellulosic-base planographic printing plates it has been common to type images with specially prepared typewriter ribbons, or write on these plates with specially prepared pencils, crayons or inks. Such cellnlosic-base planographic printing plates, often referred to in the art as direct image planographic printing plates or masters, may also be imaged by preprinting them using specially prepared preprinting inks.
Accordingly, another object of this invention is to produce a cellulosic-base planographic printing plate which can not only be used in conjunction with stylusapplied electric signals but will be useful as well for receiving an image as indicated above by typing or printing, etc.
Another object of this invention is to produce a cellulosic-base planographic printing plate having an electrically conducting basecoating, an electrically conducting intermediate coating of hydrophilic character, and a resinous top coating containing for example a vinyl acetate maleic acid copolymer or vinyl methyl, vinyl ethyl or vinyl isobutyl ether maleic acid copolymer, said top coating being rendered water resistant. l
Another object of this Vinvention is to produce a cellulosic-base planographicV printing plate having an electricallyy conducting intermediate coating of hydrophilic character and a resinous top coating containing for example a vinyl methyl, vinyl ethyl, or vinyl isobutyl ether maleic acid copolymer in which one of the acid groups of the maleic acid has been converted to a methyl or ethyl ester, said top coating being rendered water resistant.
Another object of this invention is to produce a cellulosic-base planographic printing plate having an electrically conducting base coating, an electrically conducting intermediate coating of hydrophobic character and a top coating containing a resinof the type above described, which coating has been rendered water resistant. Y
Another object of this invention is to produce a planographic printing plate in which the base support is a metal or electrically conducting paper or film to which is applied a top coating containing a resin of the type above described, which coating has been rendered Water resistant with an aluminum or ferric salt,
Y A feature of the invention relates to the novel combination of the several compositions of coatings applied 'to a ilexible backing-whereby there is produced an rf' ICC electro-sensitive image-forming blank which can also be used as a planographic master.
Another feature relates to a planographic printing plate having an exposed surface coat which is hydrophilic and water resistant andconsisting mainly of a vinyl maleic acid copolymer resin, with or without a light colored pigment.
As shown in the drawing, the recording and printing plate comprises a base 1 consisting of paper or any other pliable material or llm. To the pliable material or film is applied three coatings or layers. The coating 2 directly over the base support is formulated Yso that it not only has the correct electrical resistance to render the plate selectively responsive to stylus-applied potentials, but will also act as a water-impervious layer or water barrier which will keep the support, in the case of paper, from becoming wet and dimensionally unstable when the nished plate is dampened during the planographic printing process. The layer or coating 3, herein referred to as the intermediate coating, has the proper electrical resistance so that stylus-applied currents will perforate elemental areas in the surface of the plate leaving a clear, sharp image thereon but without perforating the base 1. The intermediate coat may be either hydrophilic or hydrophobic in character. The top layer or coating 4, referred to herein as the lithographie coating, has two purposes. The main purpose is that of serving as a lithographie surface which will attract and hold water in the non-imaged or un-recordedareas,Y as is Well-known in the art of planographic printing. The second is that of providing a coating which can be made light in color with a suitable pigment so that the dark imaged areas will be clearly visible. This contrast is not however essential to the operation of the plate. Furthermore, if desired, the intermediate coating 3 may be eliminated if a base 1 having electrical conducting properties is used. Y
As disclosed in U.S. Patent 2,664,044, the base paper or support may be of a'conducting or non-conducting type, whereby it is made electro-sensitive for the recording Vof electrical signals to make a duplicating blank by electro-optical scanning arrangements also asdisclosed in said Patent'2,664,044.v It is preferable that the support, if paper, be so treated by well-known methodsas to possess wet strength. l
In accordance with this invention the electrically conducting coating 2 comprises, for example, acetylene black or other electrically conducting carbon black, mixed withY a suitable binder such as polyvinyl chloride,pol`y vinyl acetate, acrylonitrile polymers, cellulose ethers or esters, copolymer of vinyl chloride, vinyl acetate, vinylidene chloride, polymers, etc. The binder for the intermediate layer or coating 3, the solvent for this coating, and the method of application should be such that there will be no tendency for the base coating 2 to be deleteriously alected by the application of coating 3. Furthermore, the resin, solvent and method of Vapplication ofv the lithographic coating 4l should be such that neither of the two previous coatings 2 or '3 be deleteriously affected by the application of coating 4.
Since the lithographie coating will be the one which is exposed during subsequent handling or'printing, it is important that the binder used for this coating be resistant to water or capable of being rendered water resistant by subsequent treatment, otherwise Vthe printing plate would not only spot and smear vduring handling but the lithographie coating would bedisturbed or washed away during the dampening cycle of the planographic printing process.
The following is a typical example, but not by way of limitation, of a formulation which can be used for the base coating 2. Another example is given in U.S. Pat- Y 3 ent No. 2,664,043, to Harold R. Dalton, assigned to the assignee of the persent application.
First example forvcoatng 2 30.0 grams of Vinylite VYNS (manufactured bythe Bakelite.Corporatiolnvinyl chloride-vinyl acetate copolymer-.90 percent chloride) (average molecular weight 15,000)
30.0 gramsV of acetylene black (Shawinigan Products Corporation) 400.0 gramsof methyl ethyl ketone Y v The coating is easily prepared by dissolving the Vinylite resin in the methyl ethyl ketone. The solution is poured into a yball mill jar to which is also added the acetylene Iblack. The mixture is milled for a period of 24 hours. The coating isl applied to the paper by any of the usual methods which includes spraying, dipping, knife coating, roller coating, etc. After the coating has been applied the'solvent is evaporated by heating or other suitable method leaving behind a dry smooth coating on the paper. f
The following is another example of the formulation that can be used for coating 2.
Second example for coating 2 15.0 grams V-inylite VYDR (manufactured by the Bakelite Corporation, vinyl'chloride-vinyl acetate copolymer-96 percent vinyl chloride) (average molecular weight 24,000)
15.0 grams acrylonitrile-butadiene rubber (35 percent acrylonitrile manufactured by Goodrich Tire and Rubber Co.) v
376.0 grams methyl ethyl ketone 75 .0 grams of methyl isobutyl ketone 50.0 grams acetylenejblack (Shawinigan Products Corporation) 15.0 grams di-octyl phthalate Y 6.0 grams Acrawax (octadecanoicamide) =(Glyco Products Co.)
The Vinylite resin is dissolved in a mixture of 290.0 grams of methyl ethyl ketone and 75.0 grams of methyl isobutyl ketone. The rubber is dissolved in 61 grams of methyl ethyl ketone while the Acrawax is dissolved in the remaining 25.0 grams of methyl ethyl ketone with a slight amount of heating. These solutions and the other ingredients Vare added to a ball mill jar and the mixture milled for 24 hours. This coating is applied to the paper lby any'ofthe 'methods previously named, again followed by drying.
As already stated, the intermediate coating 3 may be eitherhydrophilic or hydrophobic in character. A few examples of hydrophilic resins Vwhich can be used for the intermediate coating 3are casein, soya protein, gelatine, hydroxyethylcellulose, polyvinyl acetate, polyvinyl alcohol, etc.' A few examples of hydrophobic resins which can be used for `the intermediate coating 3 are methacrylates, methyl methacrylates, styrene, polyvinyl chloride-acetate, polyvinyl chloride, polyvinylidene chloride, urea formaldehyde,gcellulose esters and ethers, etc.
The following is a typical example of a formulation which can be used for the intermedaite coating 3 having hydrophilic properties.
First example for coating 3 (hydrophilic) 20.0 grams`Gelva C3 resin (grade V-30 modified polyvinyl acetate manufactured by Shawinigan Products Corporation) Y 20.0 grams Elvanol`20-105 resin (polyvinyl alcohol,
inigan Products Corporation) 'I'he Elvanol was dissolved in 180.0 grams of hot methanol. The Gelva is dissolved in the remaining 100.0 gramsof methanol. The two solutions and the carbons are added to a ball mill jar and milled for 24 hours. This formulation is applied over base coating 2 as already described Y'byany of the methods cited under the examples for coating 2. After the coating operation, it is necessary to evaporate again the excess solvent by heat or any other suitable method.V
The following is a formulation which can be used for the intermediate coating 3 having hydrophobic properties.
Second example for coating 3 (hydrophobic) 20.0 grams of butyl methacrylate polymer (Hypolon P-4, E. I. du Pont de Nemours Co.)
100.0 grams of Toluso (Shell Chemical Co.) 2.66 grams of gas black (Dixie No. 5, United Carbon 0.33 grams of acetylene black (Shawinigan Corp.)
The butyl methacrylate is dissolved in the Tolusol (mixture of straight chain and cyclic hydrocarbons) and added to the carbon in a ball mill jar. The mixture is milled for 24 hours. The coating is applied over the base coating 2 by means previously described and heated to drive olf the solvent and leave a dry coating.
Another example of a formulation which may be used for the intermediate layer 3 is as follows: this formulation will produce a coating having hydrophilic properties.
Third example for coating 3 (hydrophilic) 80.0 grams Protovac PV8979 (modified casein manufactured by theV Borden Co.)
560.0 grams of water 20.0 grams of formaldehyde (8 percent solution) 0.8 grams of Dowicide-G (sodium pentachlorophenolate, manufactured by Dow Chemical Co.)
12.0 cc. of ammonia (28 percent) 2.0 grams of Nopco 1497-V a water dispersion of fats and fatty acids (National Oil Products Co.)
1.33 grams of acetylene black (Shawinigan Products Corp.)
106.7 grams of gas black (Dixie No. 5, United Carbon The Protovac PV8979 is dispersed in hot water for 30 minutes under mild agitation. At this point the ammonia is added to dissolve the Protovac PV8979. When this solution has cooled, it is added to the other ingredients which are in a ball mill jar. The mixture is milled for 24 hours. This mixture is coated over the base coating 2 by any of the aforesaid methods and heated to drive olf the solvent which is water in this instance.
The resins already mentioned for use in the lithographie coating 4 can be formulated to produce a permanent bond with the intermediate coatings mentioned. In addition the lithographie coating in its final form is resistant to water and possesses a hydrophilic tendency over its entire surface as will be discusssed below. Such resins as casein, sodium alginate, gelatine, carboxylmethyl cellulose polyvinyl alcohol, etc., have been used in the past for preparing the top coatings for directl image planographic printing plates. Any one of these resins may be used in the lithographie coatings of the electro-responsive planographic printing plate described. However, the poor recording electro-sensitivity properties of these materials makes them undesirable for commercial use.
Products It has been foundthat if the resin binder used in the..y
lithographie coating is a copolymerization product of (A) vinyl acetate and maleic acid, or (B) vinyl methyl, vinyl ethyl, or vinyl isobutyl .etherV and maleic acid, or (C) vinyl methyl, vinyl ethyl, Yor vinyl isobutyl ether and ythe half methyl or ethyl ester of maleic acid, the electrosensitivity and imaging ability of the electro-responsive planographic printing plate is greatly'improved. In addition, these materials, when used in a lithographie coating, retain all of the desirable properties required of such a coating, namely a hydrophilic character over its entire surface, water resistance upon being treated after deposition, the ability to repel ink once the coating is wet, and receptivity to other imaging mediasuch as lithographie crayon when the coating is dry.
'I'lhese copolymers are easily used in the preparation of the lithographie coating since they are readily soluble in hot water or very dilute alkali. The dried coating continues to remain water soluble so that a subsequent operation is required to give the coating water resistance. It has been found that it is necessary to treat the dried lithographie coating with an insolubilizing material for example a solution of a heavy metal salt such as an aluminum salt or ferrie iron salt. These may be used in concentrations of 5 percent to 25 percent in water and applied over the top lithographie coating in amounts to give the coating the necessary water resistance.
A typical formula which may be used as a lithographie coating according to the present invention and also on direct image planographic plates may be prepared from the following materials.
F rst example for coating 4 16.0 grams of polyvinyl methyl ether-maleie anhydride copolymer (manufactured by General Aniline and Film Corporation) 48.0 grams of zinc oxide 48.0 grams of zinc sulfide 432.0 grams of Water The coating is prepared by 4dissolving the copolymer of polyvinyl methyl ether and maleie anhydride in boiling water. The solution is cooled and added to the zine pigment which has been placed in a ball mill jar. The materials are milled for 24 hours. This coating is applied over the intermediate layer 3 by any means described under the above examples and heated to drive off all the water. The dried coating is then treated with a percent water solution of a ferrie salt such for example as ferrie chloride hexahydrate by dipping, spraying, brush coating, roller coating, wire coating, air knife coating, etc., followed by the application of heat to drive olf the water remaining in the coatings and on the surface of the plate.
Another combination of materials that can serve as a lithographie coating on electro-responsive planographic printing plates is prepared as follows.
Second example for coating 4 16.0 grams of polyvinyl acetate-maleic anhydride copolymer 48.0 grams of zinc oxide 48.0 grams of zinc sulfide 336.0 grams of water 0.9 grams of sodium hydroxide The polyvinyl acetate-maleic anhydride copolymer is dissolved in Water to which the sodium hydroxide had previously been added. The solution is then placed, along with the zinc pigments, into a ball mill jar and milled for 24 hour-s. The coating is applied over the intermediate coating 3 by any of the aforementioned methods and heated to evaporate the water. When the coating is dried, it is made resistance to Water by treatment withv vinyl methyl ether-maleie anhydride to react in methanol for 24 hours at room temperature or by refluxing it with methanol until the reaction is complete.
T hiral example for coating 4 8.0 grams of polyvinyl methyl ether-maleic anhydride half methyl ester copolymer 168.0 grams of methanol 24.0 grams of zinc oxide 24.0 grams of zinc sultlde The ingredients are placed in a ball mill and milled for 24 hours. The coating is then applied over the intermediate layer 3 by any method described in previous examples aud heated to drive otf the solvent. Since the coating made using the half esters is still non-resistant to water at this point, it must be treated with a water solution of Iferrie or aluminum chloride in water' and again heated to evaporate all traces of solvent. The above mixture may also be used as a lithographie coating for direct image planographic printing plates, that is plates which are not required to be electro-sensitive.
What is claimed is:
l. A planographic printing plate comprising, a backing having an exposed Water insoluble, hydrophilic lithographic surface coat consisting mainly of a copolymer of maleic acid and one or more vinyl ethers chosen from the group consisting of vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and the half methyland half ethyl esters of the said ethers, and an electrically conductive water barrier coat containing powdered conductive carbon with a resin binder and located between 4 said backing and said lithographie surface.
2. A planographic printing plate according to claim l in which the backing comprises Wet strength paper.
3. A planographic printing plate according to claim 1 in which the backing is of wet strength paper, andin which another conductive resin coating is located between said water barrier coat and said lithographie coat.
4. A blank which is electro-sensitive to stylus-applied electric potentials to form a planographic printing master, comprising a backing of cellulosic material, an electrically conductive base coat on said backing, an electrically conductive intermediate coat, and a resinous hydrophilic, lithographie top surface coat containing a copolymer of vinyl ether and maleic acid and wherein the vinyl ether has been chosen from the group consisting of vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and the half methyl and half ethyl esters of the said ethers, said top surface coat being water resistant by having included therein an insolubilizing salt of a heavy metal.
5. A blank according to claim 4 in which said salt is a ferrie salt.
6. A blank according to claim 4 in which said salt is an aluminum salt. Y
7. A blank which is electro-sensitive to stylus-applied electric potentials to form a planographic printing master, comprising a cellulosic backing, an electrically conductive base coat on said backing, an electrically conductive intermediate resinous coat, and a resinous lithographic top surface coat which is water resistant and comprising a copolymer of a vinyl ether and maleic acid in which one of the maleie acid groups has been converted to an ester and lthe vinyl ether has been chosen from the group consisting of vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and the halfv methyl and half ethyl esters of the said ethers, said top lithographic surface coat including an insolubilizing salt of a heavy metal'to render it Water resistant.
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|U.S. Classification||101/462, 428/514|