US3552316A - Dtr offset master and composition for preparation of same - Google Patents

Dtr offset master and composition for preparation of same Download PDF

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US3552316A
US3552316A US527028A US3552316DA US3552316A US 3552316 A US3552316 A US 3552316A US 527028 A US527028 A US 527028A US 3552316D A US3552316D A US 3552316DA US 3552316 A US3552316 A US 3552316A
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weight
master
salt
offset master
silver halide
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US527028A
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Mary K Ormsbee
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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

  • n 101/4591 ABSTRACT An offset master adapted to be imaged to pro- 101/462,96/29, 6/ vide an ink receptive oleophilic image by diffusion transfer
  • InLCl B4ln 1/04 from an exposed silver halide negative in which the offset 1/ l 5/ 54 master is formed of a base sheet having a water soluble, water
  • Field ofsearch 96/29, 76 receptive hydrophihc lithographic surface on which the 101/149, 2, 456, 466, 453, 459, 462 image is deposited and which includes the combination on the lithographic surface of a nucleating agent for silver halide, a
  • References Cited sensitizing dyestuff which renders more hydrophobic and ink UNITED STATES PATENTS receptive the silver image that is formed by reduction of silver 2,352,014 6/1944 Rott 96/29 halide on the lithographic surface of the master and a water 2,81
  • 101/466 soluble salt selected from the group consisting of zirconium, 3,169,065 2/1965 Sorkin et a1 101/456 thorium and titanium, and which may include a cadmium salt 3,220,837 1 1/1965 Land et al 96/29 in addition to the zirconium, thorium or titanium salt.
  • 1 d is a o DTR OFFSET MASTER AND COMPOSITION FOR PREPARATION OF SAME
  • This invention relates to the art of offset or lithographic duplication and more particularly to a new and improved offset master and method for the preparation of same.
  • Offset masters for offset copy work are generally of the direct image type wherein the hydrophilic lithographic surface of the master is imaged directly by the application of an oleophilic ink receptive imaging material, as by inscribing with a crayon or ink, or by transfer from a carbon sheet in response to compression or impact by stylus, typewriter key, die impression or the like.
  • the non imaged portions of the master When mounted on a lithographic press and wet with an oleophilic ink composition and an aqueous repellent, the non imaged portions of the master accept the aqueous repellent while the ink composition is takenupby the oleophilic ink receptive imaged portions of the master for subsequent transfer either directly to copy sheets brought into surface contact with the inked master or indirectly to an offset blanket from which the image is transferred to copy sheets.
  • a master of the type described has been produced wherein the hydrophilic lithographic surface is overcoated with a water soluble, resin forming, light sensitive diazo compound in which a negative transparency is first formed of the original and then the diazo light sensitive coating is exposed to.the developed negative transparency to resinify the diazo compound in the exposed areas while the portions of the light sensitive diazo coating in the unexposed areas are removed by washing to produce an imaged photolithographic plate.
  • the photolithographic masters are somewhat similar in construction in that the master sheet is presensitized with a light sensitive material that is convertible to an ink receptive imaging material upon exposure to light.
  • Such presensitized photolithographic masters are subject to a number of deficiencies including high cost, short shelf life, the need to make use of specialized equipment and materials, and the need to prepare a negative transparency by conventional photographic technique.
  • lithographic or offset masters capable of being imaged by diffusion transfer technique from an exposed by undeveloped silver halide negative have been produced in which thehydrophilic, lithographic surface is provided with a nucleating or fogging agent for reducing silver halide to an ink receptive, water repellent silver image whereby, when the master sheet is brought into contact .with the exposed silver halide negative wet with a silver halide solvent and developer, the silver halide in the unexposed portions of the negative transfers by diffusion to the surface of the master where the silver halide or complex formed thereof is reduced to a silver, ink receptive, water repellent imaging material on the hydrophilic, water receptive, lithographic surface to produce the master having an image corresponding to the original.
  • the diffusion transfer reversal technique makes use of equipment and materials which are of low cost and which have heretofore found widespread use in single copy diffusion transferreversal processes commonly employed in the field.
  • the diffusion transfer process also eliminates the need for the preparation of a negative transparency and the exposure of the negative transparency to a presensitized master is also completely eliminated.
  • DTR diffusion transfer reversal
  • FIG. 1 is a schematic perspective View, partiallyin section, of a DTR offset master prepared inaccordance with the practice ofthis invention; .v t 1 5 ,1. I
  • FIG. 2 is a schematic sectionahelevational view illustrating the process of diffusion transferto formthe image on the DTR offset master of FIG. 1; and t FIG. 3 is a perspective view par l in section of the imaged master produced in accordance wlth the practice of this invention.
  • the concepts of this invention reside in the fabrication of a DTR offset master formed of a base sheet 10 having a water insoluble, water receptive, hydrophilic, lithographic surface 12 which is overcoated to deposit the combination of a silver vhalide nucleating agent, sometimes referred to as a fogging agent, and oneor more metal salts which operate to enhance the formation of the silver image, its adhesion to the lithographic surface of the master, and its ink receptivity to provide a desirable balance between the hydrophilic character of the nonimaged portions and the hydrophobic character of the imaged portions whereby aqueous repellent with which the surface of the master is wet will go to the nonimaged portions, while the oleophilic inkwill wet out-the: imaged portions for the production of copy by offset onto copy'sheets.
  • a silver vhalide nucleating agent sometimes referred to as a fogging agent
  • metal salts which operate to enhance the formation of the silver image, its adhesion to the lithographic
  • Use can be made of a base sheet formedofafoil of an amphoteric metal, such as aluminum, copper orzinc, which the surface has been treated to render the surface hydrophilic.
  • an amphoteric metal such as aluminum, copper orzinc
  • thesurface can be rendered hydrophilic by brushing, orby anodizing, oriby an acid etch, and preferably by silicating, as described in the Jewett et al.U.S. Pat. No. 2,714,066.
  • a coated paper master in which the base sheet' lfl isv a resinous treated, high wet strength paper which is provided with a water insoluble, water receptive, hydrophilic, lithographic coating formulated of a binder selected of a hydrophilic colloid such as casein, as in U.S. Pat. No. 2,534,650; carboxymethylcellulose, as in U.S. Pat. No. 2,542,784; alginates, as in U.S. Pat. No. 2,806,424; polyacrylates, as in U.S. Pat. No. 2,760,431; polyvinyl alcohol, as in U.S. Pat. No. 2,230,982; starch, polyvinyl acetate, and the like, with a suitable tiller such as zinc oxide, clay, satin white, and the like.
  • a suitable tiller such as zinc oxide, clay, satin white, and the like.
  • the base sheet is formed with openings 18 at the leading edge for use in mounting the imaged master onto the plate cylinder of a lithographic press but other means can be employed for engaging the leading edge of the imaged master for mounting onto the plate cylinder.
  • nucleating agent As the nucleating agent, best use is made of a stannous halide, such as stannous chloride, but other silver halide nucleating agents for the conversion of the dissolved silver halide into silver, in the absence of light, can be employed such as colloidal silver, cadmium sulfide, and the like nucleating or fogging agents described in U.S. Pat. No. 2,352,014.
  • a water soluble salt of zirconium, thorium and/or titanium in combination with the silver halide nucleating agent.
  • use can be made of the corresponding acetate, propionate, chloride, bromide, fluoride, and nitrate of the metals.
  • stannous halide and zirconium salt it is desirable to maintain the ratio of salts to within the range of one part by weight of the stannous salt to l to. 8 parts by weight of the zirconium salt with an optimum ratio of about i to 2.5.
  • the effect of the combination of the water soluble salts can be further improved by'the modification to include a-water the accompanying soluble cadmium salt.
  • soluble cadmium salt such as cadmium acetate, cadmium chloride, cadmium nitrate and the like, alone or in combination with an antioxidant, as described in my copending application Ser. No. 526,988 filed concurrently herewith, and entitled Offset Master for Imaging by Diffusion Transfer and Method of Preparation of Same.”
  • the materials should be applied in the same coating weight in the ratio of one part by weight of the stannous salt to l to 8 parts by weight of the zirconium salt and 0.0! to 0.5 parts by weight of the cadmium salt, and preferably one part by weight of the .stannous salt to 1.7 to 3.5 parts by weight of the zirconium salt and 0.02-to 0.2 parts by weight of the cadmium salt.
  • the desired novel effect is secured when the dyestuff is present in the composition in an amount, based upon the coating solids, within the range of 0.001 to 1.0 percent by weight and preferably 0.05 to 0.1 percent by weight.
  • the components of the overcoating may be applied from a single coating composition having a solids content within the range of 3 to percent by weight or they may be applied from separate coatings containing the ingredients in various possible combinations.
  • Example 1 Solution of zirconium acetate (13% as ZrO ml 20 Distilled water -ml- 80 Stannous chloride -g- 2 Cadmium nitrate g 0. 02 Hydroquinone monomethyl ether g 2 1% solution of Rhodamine B m1 5
  • Example 2 Solution of zirconium acetate (13% as ZrO m 40 Stannous chloride g 4 Distilled water -g- 160 Cadmium nitrate -g- 04 Hydr uinone monomethyl ether g 4 Eosin J g 01 Sodium sulfide -g- 05 Silver nitrate -g- 002
  • Example 3 Solution of zirconium acetate (13% as ZrO 20 Stannous chloride g- 3 Distilled water g- 80 Eosin OJ g- .20
  • Example 4 13% solution of zirconium chloride ml, 20 Distilled water -ml- 8O Stannous acetate -g- 2 Antioxidant g 2 Erythrosine g- 01
  • An aluminum base sheet 10 having a silicated, water receptive lithographic surface 12 is roller coated with the compositions of examples I to 4 to provide a coating weight of about .75 gram per square meter.
  • Theapplied coating 14 is either air dried or drying can be accelerated by heating to an elevated temperature of about l00200 F. to produce a finished master.
  • a coated paper direct image master formed of a high wet strength paper base sheet 10 having a lithographic coating 12 formed thereon as by a hydrophilic colloid and filler, such as described in the aforementioned patents.
  • the lithographic surface of the coated paper base sheet is overcoated with a composition of one of the examples 1 to 4 applied in an amount to provide a dry coating weight of 0.5 to 3 grams per square meter.
  • a negative 20 in the form of a base sheet 22 having a light sensitive silver halidegelatin stratum 24.
  • suitable negatives are Gevaert GS negative of Gevaert Photo Production of Antwerp, Belgium, and Anken Contact Negative of the Anken Chemical Company in the United States.
  • the negative 20 is first exposed to the original in a conventional photographic exposure apparatus. The exposed negative is then brought into pressure contact with the coated surface 14 of the master after one or both of the surfaces has been wet with a monobath developer, as represented by the following example 5:
  • the exposed negative and master cam be processed through an A. B. Dick Photocopier containing the monobath solution.
  • the monobath operates to form a soluble complex of silver halide in the unexposed portions of the negative for transfer of the silver halide by diffusion to the corresponding surface of the master where the silver halide is reduced by the materials present on the lithographic surface of the master to deposit the dense masses of silver 30 concentrated at the surface of the master, to form a highly hydrophobic, ink receptive image 32 on the lithographic hydrophilic surface.
  • the imaged master can then be swabbed, wet or otherwise washed with a conventional fixer or conditioner, such as the CT Offset Fixer of Eastman-Kodak, or 084-4966 A. B. Dick Photoplax Conditioner, which operates to make the nonimaged areas hydrophilic and to fix the image onto the master. Thereafter the imaged master can be mounted on the plate cylinder of a conventional lithographic press for sequential wetting with aqueous repellent and oleophilic ink composition whereby the nonimaged portions of the plate are wet by the repellent while the imaged portions receive ink whereby thousands of copies of good quality can be produced.
  • a conventional fixer or conditioner such as the CT Offset Fixer of Eastman-Kodak, or 084-4966 A.
  • B. Dick Photoplax Conditioner which operates to make the nonimaged areas hydrophilic and to fix the image onto the master.
  • the imaged master can be mounted on the plate cylinder of a conventional lithographic press for sequential wetting with
  • the hydrophobic character of the formed can be greatly improved by the formulation of the coating composition to include an additional amount of silver salts as additional nucleating agent. While such silver salts are not in any way equivalent to the dyestuffs, such additional nucleating agents can be incorporated without the dyestuff to give the desired result but it is preferred to make use of such additional amounts of silver salts in combination with the dyestuff of the type heretofore described.
  • additional nucleating agent use can be made of silver acetate, silver nitrate, silver sulfide and the like, as represented by the following examples:
  • Example 6 Solution of zirconium acetate (13% as ZrO ml- 2O Distilled water ml 80 1.3% solution of silver acetate -ml 40 Stannous chloride g 2
  • Example 7 Mixture A:
  • composition of example 6 or mixture B of example 7 can be coated onto the lithographic surface of an offset master in the manner and amounts previously described in examples 1 to 4.
  • the master prepared of the compositions of examples 6 and 7 can be imaged and used in the production of multiple copies by the procedures previously described in connection with the masters produced by the compositions of examples 1 to 4.
  • the image that is formed by diffusion transfer from an exposed negative will remain strongly bonded to the lithographic surface so that a large number of copies of good quality can be produced by conventional lithographic duplication technique.
  • An offset master for imaging to provide an ink receptive oleophilic image by diffusion transfer from an exposed silver halide negative comprising a base sheet having a water insoluble, water receptive, hydrophilic lithographic surface, said master having on the lithographic surface the combination of a nucleating agent for silver halide, and a dyestuff which densifies and renders more hydrophobic and ink receptive the silver image that is formed by reduction of silver halide on the lithographic surface of the master and present in an amount within the range of 0.001 to 1.0 percent by weight of the total solids and a water soluble salt of a metal selected from the group consisting of zirconium in the absence of a cadmium salt or zirconium, thorium and titanium when a cadmium salt is also present, and in which such water soluble salt is present as a component separate and apart from the nucleating agent and in an amount within the range of l to 8 parts by weight of the metal salt per one part
  • An offset master as claimed in claim 2 in which the materials are present in the ratio of one part by weight of stannous halide, l to 2.5 parts by weight of the salt, and in which the dyestuff is present in an amount within the range of 0.05 to 0.1 percent by weight.
  • An offset master as claimed in claim 1 in which the composition on the lithographic surface contains in addition a water soluble cadmium salt.
  • An offset master as claimed in claim 5 in which the materials are present in the ratio of one part by weight nucleating agent, 1 to 8 parts by weight of the metal salt, and 0.0] and 0.5 parts by weight of the cadmium salt, and in which the dyestuff is present in an amount within the range of 0.001
  • An offset master as claimed in claim 5 in which the silver halide nucleating agent is stannous halide and in which the materials are present in the ratio of one part by weight of stannous halide, l to 8 parts by weight of the metal salt and 0.01 to 0.5 parts by weight of the cadmium salt, and in which the dyestuff is present in an amount within the range of 0.001 to 1.0 percent by weight.
  • an offset master as claimed in claim 5 in which the silver halide nucleating agent is a stannous halide and in which the materials are present in the ratio of one part by weight of stannous halide, 1 to 2.5 parts by weight of the metal salt, 0.02 to 0.2 parts by weight of the cadmium salt, and in which the dyestuff is present in an amount within the range of 0.05 to 0.1 percent by weight.
US527028A 1966-02-14 1966-02-14 Dtr offset master and composition for preparation of same Expired - Lifetime US3552316A (en)

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US (2) US3552315A (xx)
BE (1) BE694055A (xx)
DE (1) DE1522477A1 (xx)
FR (1) FR1515292A (xx)
GB (1) GB1169774A (xx)
NL (1) NL6701955A (xx)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3971660A (en) * 1974-04-04 1976-07-27 Eastman Kodak Company Lithographic printing plate comprising hydrophilic layer of polyvinylacetate crosslinked with tetraethylorthosilicate
US5068165A (en) * 1989-07-25 1991-11-26 Agfa-Gevaert, N.V. Lithographic aluminum offset printing plate made according to the dtr-process
DE29701585U1 (de) * 1997-01-31 1997-03-13 Roland Man Druckmasch Druckplatte
US5815243A (en) * 1993-02-10 1998-09-29 Agfa Division, Bayer Corporation Electronic prepress apparatus for producing lithographic printing plates

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS561629B2 (xx) * 1972-02-25 1981-01-14
US3860426A (en) * 1972-12-22 1975-01-14 Eastman Kodak Co Subbed lithographic printing plate
US6014929A (en) * 1998-03-09 2000-01-18 Teng; Gary Ganghui Lithographic printing plates having a thin releasable interlayer overlying a rough substrate
GB0229090D0 (en) * 2002-12-13 2003-01-15 Eastman Kodak Co Display panel

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2352014A (en) * 1941-07-21 1944-06-20 Rott Andre Photomechanical printing process and printing material for carrying out the same
US2814988A (en) * 1954-05-19 1957-12-03 Armour Res Found Printing plates and the production thereof
BE565696A (xx) * 1955-03-31 1958-03-31
GB830623A (en) * 1956-04-18 1960-03-16 Agfa Ag A planographic printing process using greasy or fatty ink
GB856770A (en) * 1957-09-07 1960-12-21 Kalle & Co Ag Improvements in or relating to photographic reproduction
US3169065A (en) * 1960-10-11 1965-02-09 Harris Intertype Corp Method of making resist and deep etch lithographic printing plates with ferric ammonium compound sensitized plates
US3220837A (en) * 1955-07-22 1965-11-30 Polaroid Corp Diffusion transfer to stratum of a silver image inked and used in printing
US3309990A (en) * 1961-01-25 1967-03-21 Azoplate Corp Process for the preparation of printing plates
US3311473A (en) * 1962-06-28 1967-03-28 Eastman Kodak Co Silver halide diffusion process and products therefor

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2352014A (en) * 1941-07-21 1944-06-20 Rott Andre Photomechanical printing process and printing material for carrying out the same
US2814988A (en) * 1954-05-19 1957-12-03 Armour Res Found Printing plates and the production thereof
BE565696A (xx) * 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
GB830623A (en) * 1956-04-18 1960-03-16 Agfa Ag A planographic printing process using greasy or fatty ink
GB856770A (en) * 1957-09-07 1960-12-21 Kalle & Co Ag Improvements in or relating to photographic reproduction
US3169065A (en) * 1960-10-11 1965-02-09 Harris Intertype Corp Method of making resist and deep etch lithographic printing plates with ferric ammonium compound sensitized plates
US3309990A (en) * 1961-01-25 1967-03-21 Azoplate Corp Process for the preparation of printing plates
US3311473A (en) * 1962-06-28 1967-03-28 Eastman Kodak Co Silver halide diffusion process and products therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3971660A (en) * 1974-04-04 1976-07-27 Eastman Kodak Company Lithographic printing plate comprising hydrophilic layer of polyvinylacetate crosslinked with tetraethylorthosilicate
US5068165A (en) * 1989-07-25 1991-11-26 Agfa-Gevaert, N.V. Lithographic aluminum offset printing plate made according to the dtr-process
US5815243A (en) * 1993-02-10 1998-09-29 Agfa Division, Bayer Corporation Electronic prepress apparatus for producing lithographic printing plates
DE29701585U1 (de) * 1997-01-31 1997-03-13 Roland Man Druckmasch Druckplatte

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DE1522477A1 (de) 1969-08-28
US3552315A (en) 1971-01-05
FR1515292A (fr) 1968-03-01
GB1169774A (en) 1969-11-05
NL6701955A (xx) 1967-08-15
BE694055A (xx) 1967-07-17

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