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Alca. 7 15 a 7 Oct. 8, 1957 D. A NEWMAN ETAL 2,808,778 PLANOGRAPHIC PRINTING PLATE Filed Sept. 16, 1953 Alca. 7 15 A 7 A3 11 4. i g sh aii RATIO (FILLER/BINDER) INVENTORs Zougaas -4. Ave wa? , , AZara T. Sc/cotz?auer BY 2,808,778 United States Patent Office Patented Oct. 8, 1957 2 cording to the present invention it is possible to insolubilize the coating throughout without regard to its openness So 2,808,778 that the ratio of filler may be varied at will to give ratios PLANOGRAPHIC PRENTING PLATE best suited to other considerations. The product of this method of insolubilization, i.e., Douglas A. Newman, Glen Cove, and Allan T. Schlotz the method of coagulation of a carboxymethyl cellulose hauer, Locast Valley, N. Y., assignors to Columbia product with mixtures of a copper salt with an iron, alumi Ribbon & Carbon Manufacturing Company, Inc., Glen num or chromium compound, or mixtures of a copper Cove, N.Y., a corporation of New York salt with compounds of two or all of said metals has been Application September 16, 1953, Serial No. 380,446 0 determined as the most successful form of carboxymethyl cellulose deposit known to date insofar as the formation 6 Claims. (C. 101-149.2) of planographic printing surface is concerned. Up until the present invention was made, however, it was necessary to carry on this insolubilization primarily as an after This invention relates to the manufacture of plano 15 treatment applied to the dried soluble layer. The plac graphic printing plates, suitable for use in planographic ing of a self-insolubilizing layer of carboxymethyl cel printing processes in which the surface of a plate. on lulose including a copper salt was disclosed and claimed which an image is formed of ink-receptive material (e.g., in the application of Douglas A. Newman, Serial No. a waxy or greasy ink) is wetted with an aqueous ink 318,340, filed November 1, 1952, but that application repelling fountain fluid, then inked over to deposit ink 20 only on the image, the latter being then transferred to disclosed specifically a solution which was slightly alkaline a sheet of paper, usually by way of a blanket as in offset in pH to maintain the copper salts in solution, and which printing, the image being repeatedly reinked and the would throw down the known suitable coagulant iron foundation being maintained wet and hence ink-repellent and aluminum compounds, if present, as precipitates with 25 out giving a chance for their reaction with the carboxy as repeated copies are printed. methyl cellulose. - In the following specification and claims where it is The present invention has for its object the preparation found necessary to refer to coating thicknesses the same of a planographic plate from a coating solution of car are expressed in terms of pounds per ream, and will be boxymethyl cellulose which is self-insolubilizing on dry understood to refer to a ream of 500 sheets, 25' X 38'. ing and which, at the same time, includes reagents of More specifically this invention relates to planographic 30 such character that the resulting layer will still be made printing sheets or plates having a paper foundation in up of the copper derivative of carboxymethyl cellulose which the printing surface is in the form of a film applied mixed with the iron, aluminum or chromium derivatives to the paper foundation and in which the surface film or mixtures thereof in the desired proportions. has greater flexibility and homogeneity and less curling Inasmuch as the cost of making planographic plates tendency than that of prior sheets, and in which the 35 depends largely upon the number of treating steps to sheet lends itself to the improved retention of certain which they must be subjected, it is another object of the types of planographic images presently regarded as some present invention to provide a paper planographic print what difficult of attachment to coated paper printing Sur ing plate in which the surface coating is of metal sub faces, as well as to improved surface retention of the ink stituted compounds of carboxymethyl cellulose of the repellent moisture. - 40 appropriate mixture for producing printed copies of the The invention, in certain of its aspects, relates to the highest quality, but a coating which is still of such a manufacture of plates in which the printing surface layer nature that it can be applied in a single coating opera comprises essentially carboxymethyl cellulose compounds tion rendering a film which automatically becomes water and a filler of china clay or the like similar to the plates 45 insoluble upon drying so that a single coating treatment disclosed in the prior application of Douglas A. Newman, is involved in applying the insoluble surface layer. Serial No. 637,088, filed December 22, 1945, now It is a feature of this invention that carboxymethyl cellu Patent No. 2,655,864. In said application is disclosed lose coatings of Self-insolubilizing nature made to con the method of making a plate, and the plate itself, in form to the viscosities, surface tensions and filler per which the printing surface or coating is of an initially solu 50 centages found in the disclosure of said Newman applica ble carboxymethyl cellulose compound which is dried and tion, Serial No. 318,340, for the purpose of providing a rendered insoluble by an after treatment with an aqueous treatment for pre-imaged sheets to convert them into solution including a copper salt, an iron salt, an alumi copy-producing masters, can be made to include the pre num salt, or a chromium compound, or mixtures of a ferred aluminum ferric and chromium insolubilization copper salt with certain of the others. This procedure 55 factors in proper proportion, in addition to the copper has resulted in the production of commercially accepta ions therein disclosed. ble printing plates which include a surface of a carboxy lt has been discovered that planographic surface coat methyl cellulose compound. While the plates and the ings as heretofore constructed, in some instances, are prints produced thereby were of good commercial quality, Subject in some degree to difficulties such as cracking, certain problems relating to their manufacture and use 60 during flexure, shattering under a type blow, flaking, were experienced which it is the object of this invention picking and the like. Another difficulty which is somc. to overconne. times experienced is that of excessive absorptivity of the The method of insolubilization of the printing surface printing layer and underlying layers so that moistening coating employed in constructing plates according to the fluids tend to drain rapidly away from the surface in teachings of said application rendered it important to in the background areas and leave the same dry after any clude in the surface coating a ratio of clay or other suita slight interruption in printing. All of these difficulties, it ble filler to the carboxymethyl cellulose binder of about has been discovered, stem primarily from the percentage 4:1, or preferably greater. These ratios were found of filler which the coating must carry, and the thickness preferable in Crder that the coating might have a suffi of the coating. However, as previously pointed out, a cient degree of openness to take up the insolubilizing 70 certain percentage of filler has been heretofore required solution and distribute it as nearly as possible to all parts in printing surfaces of carboxymethyl cellulose to insure of the carboxymethyl cellulose in the surface layer. Ac proper insolubilization by the most desirable treatments 2,808,778 3 4. known from the standpoint of producing good plano paper planographic plate which has a thickness corre graphic properties. However, without particular regard sponding to a coating weight of less than 6 pounds per to the nature of the insolubilization treatment required by ream, and in the preferred case less than 4 pounds per the binding ingredient, it is also known that with plano Ca graphic layers as heretofore commonly used, certain filler One of the important advantages of the thin surface percentages were essential in-order to provide proper ac coatings of the present invention is that the image, instead ceptance of certain types of images, especially those pro of being impressed on and attaching itself to the surface duced by carbon paper, and that drastic reduction in-filler coating of the plate, may be so placed that it appears to percentages, even if otherwise permissible, were not allow penetrate and probably does penetrate the coating and be able because the power of the surface to accept and 0. comes firmly attached to an underlying oleophilic layer retain such images would be adversely affected beyond the its degree of attachment to the plate thus being controlled point of commercial acceptability. 2. - primarily by the characteristics of the underlying layer Similarly, attempts to cause the printing layer to be without placing particular reliance on the characteristics made thinner than ordinarily deposited (e.g., in the neigh of the surface layer. To this end it is still another object borhood of 8 pounds minimum per ream) principally 5 of the invention to provide a planographic printing plate for reasons of economy, resulted in failure because the having an image-receptive, moisture-resistant undercoat coatings with usual paper-making equipment and pro ing, and a thin surface coating including a hydrophilic cedures could not be sufficiently uniformly deposited to binder of a thickness corresponding to a coating weight cover all parts of a sheet equally. In many cases the of less than 6 pounds per ream and in the preferred case areas of show-through of the oleophilic foundation or 20 less than 4 pounds per ream.
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