US3557696A - Planographic printing plate with nucleating agent and zirconium salt - Google Patents

Planographic printing plate with nucleating agent and zirconium salt Download PDF

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Publication number
US3557696A
US3557696A US564758A US3557696DA US3557696A US 3557696 A US3557696 A US 3557696A US 564758 A US564758 A US 564758A US 3557696D A US3557696D A US 3557696DA US 3557696 A US3557696 A US 3557696A
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United States
Prior art keywords
plate
image
nucleating agent
salt
copy
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US564758A
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English (en)
Inventor
Stasel Keith Hoover
James Thomas Crawford Knowles
Wong Kwong Fa Wong Yan Man
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AB Dick Co
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AB Dick Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G03F7/07—Silver salts used for diffusion transfer

Definitions

  • PLANOGRAPI-IIC PRINTING PLATE WITH NUCLEATING AGENT AND ZIRCONIUM SALT This invention is concerned with improvements in or relating to planographic printing. In particular the invention is concerned with the provision and use of a planographic printing plate.
  • planographic printing one employs a printing plate having an oleophilic image superimposed on a hydrophilic background so that on application of a greasy ink to the plate wetted with water the ink preferentially coats the image and the coated image may be used to produce copies by an offset procedure. It is possible to manufacture planographic printing plates having metal bases, the resultant plates being capable of producing tens of thousands of copies, or alternatively where at most only a few hundred copies are required it is more economic to employ the cheaper paper based plates. Plates of other materials, e.g., polyesters have also been proposed.
  • This process comprises contacting a positive paper with an exposed negative having a latent image in the presence of a developing and a fixing solution containing a silver halide solvent, whereby the latent image on the negative transfers to the positive and is developed and fixed thereon by the solution.
  • a process has also been proposed in which a paper base planographic printing plate is imaged by a diffusion transfer process in which a special negative paper is exposed to the original and the exposed negative is processed or developed with a special developer solution.
  • the emulsion on the negative paper consists of gelatin, silver halide such as silver bromide and other materials.
  • the light exposed, developed portions of the negative are partially insolubilized and incapable of transferring while the unexposed portions corresponding to the image to be reproduced will transfer on contact from the negative to the paper master surface. This is not a true diffusion transfer process because the colored reduced silver is formed in the gelatin layer, transferring to the master along with the gelatin film.
  • a method of producing a planographic printing plate which comprises applying to a base sheet having a water-insoluble, water-receptive, hydrophilic, lithographic surface, an aqueous solution of a silver halide nucleating agent and a metal salt, said metal salt being a salt of thorium, titanium or zirconium, said solution, if desired also containing a stabilizing amount of a water-soluble compatible stabilizing agent to inhibit degradation of the nucleating agent and the salt, whereby said surface is rendered imageable -by the silver halide diffusion transfer process.
  • the base sheet may be of any material used in the production of planographic printing plates, e.g., paper or commercially available metal plates. Where the base sheet is a paper base, the paper preferably has a dry Dennison Wax pick of at least six and preferably over eight.
  • the plate After the plate has dried it is ready for imaging, either for example by a typewriter, pen or pencil, or alternatively in a conventional silver salt diffusion transfer photocopying procedure from an existing image.
  • the process can be used for the reproduction of line or dot-type material and can also be used together with half tone and continuous tone screens in the preparation of the transfer negative.
  • a diffusion transfer negative is provided with a negative latent image, by exposure of an original in a photocopy machine, and the exposed negative is passed through the developing section of the machine, containing an offset developer, in contact with the planographic printing plate according to the invention so that the latent negative image on the transfer negative diffuses, on development, to the surface of the printing plate of the invention which has been treated with the aqueous solution of nucleating agent and metal salt.
  • the image is fixed, simply by applying a fixing solution and the printing plate is then ready for use on a conventional offset printing machine after fixing the image.
  • Coated papers having a lithographic surface, a good wet strength and a dry Dennison Wax pick of eight or higher and preferably above,l1 may conveniently be used as the base sheet.
  • the pick resistance be over eight.
  • binders such as casein, starch, carboxymethyl cellulose, polyacrylic acid, polyvinyl acetate, alginic acid, polyvinyl pyrrolidone and polyvinyl chloride may be used providing they form a lithographic surface when mixed with a hydrophilic filler.
  • casein has been found to provide the best results.
  • the binder may be used as such but is preferably used together with a pigment.
  • Planographic printing plates according to the invention may be manufactured from the papers termed in the trade as Art Papers, i.e., papers already coated with a binder and filler, provided the surface of the paper has a dry Dennison Wax pick of at least six and is lithographic.
  • the planographic printing plates may also be prepared from direct image[ paper base planographic printing plates provided these have been coated and filled as described. These plates may then be coated with an aqueous solution of nucleating agent and metal salt as described.
  • These paper base plates which were primarily intended for use as direct image masters for imaging, e.g., using a typewriter, generally consist of a high wet strength paper coated with a pigment, e.g., clay or zinc oxide and a binder, e.g., casein.
  • the surface of these masters is already lithographic, having been so rendered by any of the conventional methods such as by brushing or treatment with a salt, e.g., zinc chloride.
  • planographic printing plates according to the invention may be manufactured by conventional techniques and the metal salt and nucleating agent may be applied at a suitable point during manufacture, i.e., not necessarily after the plate is otherwise finished. Where a proper base is employed the metal salt and nucleating agent may thus be applied before or after a calendering step and before or after the application of a wash coat.
  • the aqueous composition used in the present invention also preferably contains a stabilizing agent, as stated, in order to prevent deterioration of the composition on the base sheet. lf the base sheet is to bestored for any length of time then the presence of the stabilizing agent may be essential in order to achieve good printing results. Thus, in the absence of the stabilizer under such conditions, a water impermeable coating is formed on the base sheet and this reduces the hydrophilic properties of the latter which are necessary to the success of planographic printing.
  • Any convenient stabilizing agent may be used always provided it is sufficiently soluble in water and does not oxidize silver.
  • suitable stabilizing agents include strong nonoxidizing acids such as dilute mineral acids, e.g., dilute hydrochloric acid or dilute nitric acid and also compatible soluble phenols such as phenol itself, quinol, pyrogallol, phluoroglucinol or resorcinol.
  • strong nonoxidizing acids such as dilute mineral acids, e.g., dilute hydrochloric acid or dilute nitric acid
  • compatible soluble phenols such as phenol itself, quinol, pyrogallol, phluoroglucinol or resorcinol.
  • polyhydric phenols with orthoor para-hydroxy groups and their ethers are antioxidants.
  • antioxidants examples include gallic acid and lower alkyl esters thereof, catechol, various ethers of quinol (e.g., lower alkyl and benzyl ethers) and quinone.
  • Various phenols are unsatisfactory owing to incompatibility with the composition, e.g., due to their forming insoluble precipitates with the nucleating agent or the metal salt or by being per se not sufficiently soluble soluble.
  • Nucleating agents for silver halides in diffusion transfer processes are known for example from US. Pat. No. 2,352,014 and British Pat. No. 614,155 and are able to reduce silver halides in the absence of light. They are also known as fogging agents.
  • the preferred nucleating agents are the stannous halides, e.g., stannous chloride, fluoride or bromide particularly stannous chloride.
  • the nucleating agent and metal sat salt may be coated onto the base sheet from two separate solutions, one of which may conveniently contain the stabilizers, antioxidants or pigments etc.
  • lithographic paper base sheets are already commercially available and further since the nucleating agent and metal salt are prone to degradation as stated, it may be preferable to treat the surface of e.g., a direct image master or an Art Paper with the aqueous solution just prior to imaging by the diffusion transfer process.
  • an aqueous solution comprising a silver halide fogging or nucleating agent and a salt of thorium, titanium or zirconium (the metal salt).
  • the fogging agent and the metal salt can also be applied to the base sheet in separate solutions and if the master is not to be used reasonably soon thereafter the water compatible stabilizer may be incorporated into one or other of the solutions preferably into the metal salt solution. In any case a short period should be allowed in between applying the solutions, and also before the master is used, to allow it to dry off.
  • the air dry weight of the coating of nucleating agent, metal salt, and stabilizer when present is variable over a wide range, e.g., from 0.6 to 16 grams per square metre.
  • a preferred range for the weight of the coating is 0.6 to 14 g.s.m.
  • the optimum coating weight will depend on the nature of various factors including the ability of the substrate to absorb the aqueous solution.
  • absorbent base sheets e.g., absorbent papers
  • preliminary trial and error experiment will soon indicate the optimum coating weight.
  • coating weights of from 0.6 to 3 g.s.m. are convenient and for more absorbent base sheets, especially certain papers, not less than 2.45 g.s.m., e.g., 5 to 9 preferably 6 to 8 g.s.m. may be used.
  • the amount of stabilizer used will depend on the required shelf life of the master but will generally be at least 10 percent and not more than 60 percent by weight of the coating. Satisfactory results can be obtained in most instances by using about 50 percent.
  • the ratio by weight of nucleating agent to metal salt in the coating may be with the range of from l.0:O.87 to l.O:l0.4, e.g., from 1.0:l.0 or 1.0:] .3 up to l.0:2.0 or 1.020.87 to 1.8:;064, l.O:5.2 and a particularly preferred ratio being about I.
  • nucleating agent or metal salt will result in a brown nonink receptive image whilst too much nucleating agent will initially produce a dense bronzy image on the master but an image which is easily washed off during the fixing and etching processes. This has been attributed to the film forming properties of the metal salt used.
  • the actual amount of nucleating agent, metal salt and optionally stabilizer in the aqueous cooling solution or solutions is thus adapted to provide an air dried coating having the characteristics set forth above.
  • the solution must not be of such a concentration that the compounds in the solution are liable to precipitate at room temperature. Conversely if the dilution is too great an excessive amount of the solution will have to be applied.
  • the preferred concentration of the compounds in the aqueous solution depends on the desired coating weight and the solubility of the constituents but may conveniently be from 2.6 percent to 17 percent by weight. Particularly preferred weight percentages for the concentration of the coating solution are from 5.25 percent to 9.6 percent and especially from 6.25 percent to 8.6 percent by weight. In the solution the ratio by weight of nucleating agent to metal salts and the amount of stabilizer will be as for the respective amounts in the coating to be laid down on the base sheet.
  • the metal salt used may be an acetate, chloride or nitrate, e.g., zirconyl acetate, zirconyl nitrate, thorium nitrate, thorium chloride, titanium dichloride or zirconyl chloride.
  • the metal salt used must not be one which destroys the lithographic properties of the surface of the master.
  • the diffusion transfer negative used is of the conventional type and may be one of those commercially available and intended for use in the production of single copies by the diffusion transfer method.
  • Gevart GS Gavart Photo Production Antwerp, Belgium
  • Oricopy Oriental Photocopy Company, Tokyo, Japan
  • Anken Photo Rapid negative made by Anken Chemical Company, New Jersey, USA.
  • the developer used may be any of the conventional offsettype developers. These are reducing solutions which contain a solvent for the silver halide, a synthetic gum, an antioxidant and other stabilizers.
  • a typical example is the offset developer made for the Diffusion Transfer Process by Gevart and also A. B. Dicks developer formula 59B9.2. 9.2.
  • the fixing solution is again conventional and may for example be CT Offset Fixer made by Kodak (Trade Mark).
  • This fixer appears to contain inter alia carboxy methyl cellulose, sodium nitrate, sodium thiosulfate, ammonium phosphate, ethyl alcohol a small amount of a mercapto compound and water. Solutions of this type are described in British Pat. No. 934,691.
  • the base sheets used were commercial wet strength papers coated with a pigment and a binder as specified.
  • the surface of the paper was then made lithographic by conventional means, e.g., by brushing or washing with a salt such as zinc chloride.
  • the solution was applied by conventional coating means such that the air dried coating weight was 6 to 8 grams per square metre.
  • the coated and dried sheet was then calendered until the surface was smooth and the sheet flat.
  • the paper master so made, was contacted with a properly exposed Gevart type GS negative sheet and passed through Gevart Offset Developer solution of the instructed dilution in an A. B. Dick M. 120 Photocopier. After about 14 seconds the two sheets were separated.
  • the image on the master was fixed by applying a Kodak (Trade Mark) CT Offset developer solution using a cotton pad. The imaged master was then used to produce copies on a conventional offset duplicator.
  • the wet strength papers coated as above can give up to 2,000 good copies.
  • Table II gives the results obtained when example 2 was repeated using other metal salts according to the invention in place of zirconyl acetate:
  • Titanium chloride Across Fair bronzy image. Fair to good copy. 15 Zirconyl chloride Uneven transfer. Fair to good copy. Image bronzy in some areas. 16 Zirconyl chloride heated one hour at 100 0.7-8 Fairly dense bronzy image. Fair to good copy.
  • Table IV shows the effect using varying quantities of stabil izer according to the present invention.
  • Examples 31-33 usethe paper and solution of example 25 and examples 34-36 the length of time required to evaluate preservatives.
  • a plate as claimed in claim 1 having a paper base, said base having a coating of an organic binder and a filler on the surface thereof and having a dry Dennison wax pick of at least SIX.
  • a plate as claimed in claim 1 wherein said metal salt is zirconyl acetate, zirconyl nitrate or zirconyl chloride.
  • agent isastannous halide.
  • lithographic masters having, for example, metal or plastic substrates may be used.
  • An example of a plastic base master is the 8.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)
US564758A 1965-07-20 1966-07-13 Planographic printing plate with nucleating agent and zirconium salt Expired - Lifetime US3557696A (en)

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Application Number Priority Date Filing Date Title
GB30857/65A GB1155596A (en) 1965-07-20 1965-07-20 Improvements in or relating to Planographic Printing Plate Blanks

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US3557696A true US3557696A (en) 1971-01-26

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US (1) US3557696A (enrdf_load_stackoverflow)
BE (1) BE684431A (enrdf_load_stackoverflow)
DE (1) DE1522476A1 (enrdf_load_stackoverflow)
GB (1) GB1155596A (enrdf_load_stackoverflow)
NL (1) NL6610206A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3640221A (en) * 1970-02-11 1972-02-08 Litton Business Systems Inc Planographic printing plate
US3736872A (en) * 1971-01-04 1973-06-05 Eastman Kodak Co Lithographic printing plate and process
US3929481A (en) * 1972-02-25 1975-12-30 Fuji Photo Film Co Ltd Etch bleaching processes for making lithographic printing plates using silver halide and/or diffusion transfer layers and a hydrophilic layer
RU2244631C2 (ru) * 2003-04-03 2005-01-20 Гершбейн Александр Михайлович Способ получения изображения и печатная краска для осуществления этого способа (варианты)
CN115243896A (zh) * 2020-03-04 2022-10-25 爱克发胶印有限公司 平版印刷版前体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE565696A (enrdf_load_stackoverflow) * 1955-03-31 1958-03-31
US3220837A (en) * 1955-07-22 1965-11-30 Polaroid Corp Diffusion transfer to stratum of a silver image inked and used in printing

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE565696A (enrdf_load_stackoverflow) * 1955-03-31 1958-03-31
US3220837A (en) * 1955-07-22 1965-11-30 Polaroid Corp Diffusion transfer to stratum of a silver image inked and used in printing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Mashev, THE TECHNOLIGY OF COATED AND PROCESSED PAPER *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3640221A (en) * 1970-02-11 1972-02-08 Litton Business Systems Inc Planographic printing plate
US3736872A (en) * 1971-01-04 1973-06-05 Eastman Kodak Co Lithographic printing plate and process
US3929481A (en) * 1972-02-25 1975-12-30 Fuji Photo Film Co Ltd Etch bleaching processes for making lithographic printing plates using silver halide and/or diffusion transfer layers and a hydrophilic layer
RU2244631C2 (ru) * 2003-04-03 2005-01-20 Гершбейн Александр Михайлович Способ получения изображения и печатная краска для осуществления этого способа (варианты)
CN115243896A (zh) * 2020-03-04 2022-10-25 爱克发胶印有限公司 平版印刷版前体

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GB1155596A (en) 1969-06-18
NL6610206A (enrdf_load_stackoverflow) 1967-01-23
BE684431A (enrdf_load_stackoverflow) 1967-01-20
DE1522476A1 (de) 1969-11-20

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