US3914125A - Diffusion transfer element and method of using same - Google Patents

Diffusion transfer element and method of using same Download PDF

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Publication number
US3914125A
US3914125A US397986A US39798664A US3914125A US 3914125 A US3914125 A US 3914125A US 397986 A US397986 A US 397986A US 39798664 A US39798664 A US 39798664A US 3914125 A US3914125 A US 3914125A
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areas
hydrophilic layer
reduction
organophilic
hydrophilic
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US397986A
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English (en)
Inventor
Tore Eikvar
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority to US397986A priority Critical patent/US3914125A/en
Priority to FR31907A priority patent/FR1459918A/fr
Priority to DE19651797524 priority patent/DE1797524C3/de
Priority to GB38810/65A priority patent/GB1129366A/en
Priority to DE1447968A priority patent/DE1447968C3/de
Priority to BE669880D priority patent/BE669880A/xx
Priority to GB27986/68A priority patent/GB1133856A/en
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Publication of US3914125A publication Critical patent/US3914125A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/26—Electrographic processes using a charge pattern for the production of printing plates for non-xerographic printing processes
    • G03G13/28—Planographic printing plates

Definitions

  • ABSTRACT 96/29 96/29 An element with a base sheet having an organophilic 96/33; 96/76 117/8; surface, an hydrophilic, liquid permeable layer on the 204/18 organophilic surface capable of becoming friable on 101/457; 101/463 reduction therein of metal ions to metal, which layer f 8 G030 contains a metal ion reduction promoter is used in the Fleld 0f Sealdl 1 formation of lithographic plates by diffusion transfer o electrolytic processes 5 References Cited 15 Claims, 2 Drawing Figures UNITED STATES PATENTS 2,774,667 12/1956 Land et a1 96/29 US. Patent 00:. 21, 1975 3,914,125
  • This invention relates to lithographic printing and more particularly to a photolithographic-image receptor sheet and to the method for making same.
  • photolithography In a field of lithography which has attained more or less separate status, ordinary or actinic light is employed as the imaging means.
  • Photolithography is related to photography in that, in both, light is used to define an image (often latent) within a light reactive material which is thereafter processed .by various chemical and/or physical means to produce, in the case of photography, a viewable image, and in the caseof photolithography a printable image (wherein, on a lithographic press, some areas will take ink and others will not).
  • the silver salt diffusion transfer process was not applicable per se to the photolithographic artin that the silver metal, when transferred to a background. material, did not alter the wetting properties of the background material as required for lithographic printing (although it did provide a satisfactory viewable, i.e., hotographic, image).
  • FIG. 1 shows one embodiment of my invention in broken-away edge view at various stages of its manufacture, and also illustrating light-exposure of the plate, processing and development of yield a lithographic plate.
  • a base sheet 10 having an organophilic surface.
  • a hydrophilic layer 11 Coated over the orgarophilic surface is a hydrophilic layer 11, which is firmly adherently bonded to the organophilic surface.
  • the hydrophilic layer is liquid permeable throughout its depth, and is characterized in becoming weak or friable upon the in situ reduction therein of metal ions, for example silver ions, to their metallic state and subsequent removal of the reduction product.
  • the hydrophilic layer contains at and immediately adjacent the interface between the hydrophilic layer and the organophilic surface, an interfacial area designated as 12, of a metal-ion reduction-promoter.
  • Stage B Under Stage B is shown the structure at Stage A to which has been added a coating 13 of a high contrast photographic emulsion.
  • the emulsion layer 13 may be a conventional preformed photographic film which has been light-exposed to an image (but not developed), or it may be an adherent cast light-sensitive emulsion coating. The latter variant is preferred.
  • Stage C Under Stage C is shown the structure at Stage B after light-exposure thereof to an image.
  • the silver compound in the emulsion layer 13 is converted into a latent reduced state, in areas 13a, while remaining unexposed and still light-sensitive in areas 13b.
  • Stage D Under Stage D is shown the structure at Stage C after it has been immersed in a developer solution.
  • the silver compound in the light-struck areas 13a is now reduced to the metallic state and is a visible black color.
  • the soluble silver halide previously present in the areas 13b has transferred or diffused along with the developing solution through the layer 11 and into contact with the metal ion reduction promoter at the interfacial areas 12b where the silver is reduced to the metallic state.
  • the reduction of the silver in the interfacial areas 12b ordinarily takes place a few seconds later than in the light-exposed areas of the emulsion layer 13a, so that, as the plate is developed an image (which is negative with respect to the original) will first appear in black in areas 13a, following which the entire viewable surface of the plate will appear black as the silver isreduced to the metallic state in the interfacial areas Under Stage E is shown the partially processed plate at Stage D after the plate has been further processed and rubbed down lightly.
  • the entire emulsion layer 13 has been removed, and the hydrophilic layer in areas 11b (as defined by and including the silver image of areas 12b) has also been removed to lay bare the underlying organophilic surface areas b of the base sheet.
  • the areas 11a (including the areas 12a) of the hydrophilic surface remain firmly bonded to the base sheet to make up the non-printing background areas of the plate whereas the exposed areas 10b of the organophilic surface make up the ink-receptive printing image areas of the plate.
  • FIG. 2 shows an alternative embodiment of the present invention in broken-away edge view of the various stages of process to form a lighographic plate.
  • Stage A it comprises a sheet 20 having a conductive metal surface 20 over which is coated a firmly bonded organophilic layer 21 which is photoconductive, e.g., which contains photoconductive material.
  • a layer of liquid permeable hydrophilic material 22 is coated on a firmly bonded organophilic layer 21 which is photoconductive, e.g., which contains photoconductive material.
  • the photoconductive material contained in layer 21 serves as the metal ion reduction promoter.
  • Stage C the structure of Stage B is shown after the plate has been connected to an electric potential (with metal surface 20 and electrically conductive area 21a serving as the cathode) in the presence of an electrolyte containing reducible metal ions (e.g., silver ions).
  • an electrolyte containing reducible metal ions e.g., silver ions
  • the silver ions come into contact with and deposit upon the cathode surface of areas 21a and become reduced to their metallic state ene resin and an additional one-half mil polypropylene resin, (said support sheet being available'from Riverside Paper Corporation, Appleton, Wisconsin) was corona discharge treated for adhesion.
  • the treated sup- H port sheet was coated with an 8 micron (0.00032inch thick organophilic dry layer from a solution containing 48% solids by weight of Union Carbides Vinylite VAGH vinyl chloride-acetate resin and American Cyanamids Unitane OR350 (titaniumdioxide) pigment in a ratio of 2.65 parts Ti0 to 1 part by weight VAGI-I resin.
  • Stage D is shown the structure of Stage C after further processing to remove the deposited silver of image 23 and the overlying hydrophilic layer at 22a to lay bare the underlying organophilic surface in areas 21a and thereby to define an ink receptive printing image.
  • the remaining areas 22b of the hydrophilic layer 22 remain firmly bonded to define the hydrophilic background areas of the plate.
  • the letter b is used to denote areas corresponding to the dark areas of the original and small letter a is used to denote areas corresponding to the light areas of the original.
  • the resulting plate has b areas as the printing areas and the a as the background areas, i.e., is a positive acting plate; whereas the embodiment shown in FIG. 2 has the b areas as the background areas and the a areas as the printing areas, i.e., is a negative acting plate.
  • EXAMPLE 1 A support sheet composed of bleached paper coated with one-half mil (0.0005 inch low density polyethylsolution by ball milling for. 48 hours and the pigmented solution in methyl ethyl ketone solvent was coated on the support sheet and dried at 150F. for 5 minutes.
  • hydrophilic silica layer Over the organophilic coating was applied a hydrophilic silica layer, in two parts.
  • the first part or sub layer was comprised of 0.1 micron thick dry coatingof collodial silica and colloidalsilver whose formulation was:
  • the sub-layer was dried for 20 seconds at 150F. and" then overcoated with the second part comprised of a 0.2-0.8 micron thick dry' coating of the following 001-: loidal silica formulation:
  • a 10 inch X 16 inch sheet of the above material was placed on the vacuum back of a Robertson 320 process camera fitted with an image reversal lens. The plate was then exposed to a right reading, positive, line copy original at a 32 f stop for 8 seconds. The exposed plate was then immersed for 30 seconds at 72F. in a tray of diffusion transfer developer with the following composition:
  • This bleaching step leached out the silver metal from the hydrophilic layer, and the remaining bleach solution was removed by water rinsing the plate.
  • the plate was then gently swabbed during rinsing with a cotton pad which cleanly removed the silica from the image areas to lay bare the underlying ink receptive organophilic surface.
  • the remaining silica layer of the nonimage areas remained firmly bonded to the organophilic surface to provide the ink-repellant background areas of the plate.
  • the plate was then ready for the press and upon test running, several hundred faithful copiess were produced.
  • the properties assumed by the image area of the silica which enables its easy removal to bare the underlying organophilic surface is the result of properly controlling the reduction of the silver halide within the hydrophilic layer.
  • the hydrophilic layer is necessarily relatively tough and securely bonded to the organophilic layer.
  • the bond between the silica and the organophilic layer within the image areas must be ruptured if the silica in said image areas is to be preferentially removed by light rubbing. This rupturing is believed to be accomplished by providing for penetration of the silver halide solution to the interface between layers and 11 to there become reduced by the silver reduction nuclei.
  • the forming of the silver metal crystals causes the desired rupturing of the silica bond and when the silver is removed by the bleaching solution, the remaining loosely bonded particles of the silica within the image areas can be cleanly broken away and easily removed to lay bare the underlying organophilic surface, without disturbing the silica of the background areas.
  • EXAMPLE 2 The same support sheet and pigmented vinyl resin coating was used as in Example 1. The support sheet with coating was further overcoated with a 0.2-0.8 micron thick dry layer of colloidal silica and colloidal silver which is coated out of an aqueous solution and dried 20 seconds at F., and whose formulation is:
  • Example 2 The same high contrast photographic emulsion as in Example 1 was'coated over the hydrophilic layer and a 10 inch X 1 6 inch sheet of the composite material was exposed and processed in the same manner as described for Example 1. This resulted in the removal of the hydrophilic silica layer in the non-light-struck (image) areas thereby to lay bare the underlying organophilic printing surface. The plate was then ready for the press and upon test running produced several hundred faithful copies.
  • the silver reduction nuclei while being present at the interface of the hydrophilic layer and the organophilic layer, are not concentrated only at the interface, but extend throughout the hydrophilic layer.
  • the glycerine inhibitor serves to insure that a substantial reduction of the metal ions takes place at the interface to effect an adequate rupturing of the bond between the hydrophilic and organophilic layers whereby the hydrophilic layer will be broken-away cleanly in the area defined in the printing image.
  • the hydrophilic silica layer tends to change in character so as prematurely to cause reduction of the silver ions to their metallic state resulting in too few of the silver ions being reduced at the interface.
  • it is difficult to process the plate so that the hydrophilic material is cleanly and thoroughly removed in the image areas, resulting in a blinded image.
  • the presence of the glycerin in the present Example serves adequately to inhibit premature reduction of the silver, even after the plate has been stored for weeks or months before use.
  • the glycerin employed as the stabilizing inhibitor in the present Example will be seen to be a hygroscopic material, i.e., a humectant.
  • humectants exhibit similar properties, and find use in connection with the present invention.
  • the latent image was formed by light-exposure of a photographic emulsion that was coated over the silica.
  • This type of embodiment of the invention provides a single sheet photolithographic plate which has certain advantages over a multiple sheet construction wherein the photographic emulsion is incorporated in separate sheeting.
  • the single sheet construction is easier to package, it insures intimate contact between the emulsion and the hydrophilic layer, it enables the manufacturer of the plate to maintain control of the type of emulsion that is used, i.e., so that the most suitable type of photographic emulsion for a particular receptor sheet is used, and a savings in cost is realized in that it only requires a single backing, whereas a separate emulsion layer requires a separate backing.
  • the steps which must be performed by a plate maker or lithographer are reduced to where all he need do is remove the plate from its light-proof container, and expose and process it.
  • the present invention is also applicable to a two sheet. structure wherein the photographic emulsion is omitted from the plate and carried by a separate film carrier, e.g., a conventional photographic film.
  • a separate film carrier e.g., a conventional photographic film.
  • the latent image can be formed by exposure on the photographic film, and development is effected in the plate structure as illustrated in the following example.
  • This pigmented solution is methyl ethyl ketone solvent was coated on the Mylar base material and dried at 150F. for 5 minutes.
  • coated support sheet was further overcoated from aqueous solution with a 0.2-0.8 micron thick dry layer of colloidal silica and colloidal silver of the following formulation:
  • a inch X 16 inch sheet of photographic film (Dinoline Acetate Ortho) was exposed without reversal to a right reading positive, line copy original and then wetted with the developer solution of the preceding example.
  • the emulsion side thereof was positioned over and in intimate contact with the receptor sheet.
  • the two-sheets were peeled apart and the receptor sheet bleached and rinsed and rubbed lightly in the same manner as described in Example 1.
  • the plate was then ready for the press and upon test running produced several thousand faithful copies.
  • the EXAMPLE 4 A support sheet comprised of a 69 lb. Crocker Hamilton paper was laminated to a 0.3 mil aluminumwhich in turn was overcoated with 2.5 to 3.0 grams per square foot (dry weight) of an organophilic photoconductive layer of the following formulation:
  • a sheet structure suitable forprinting photolithographically, comprising a base sheet having an organophilic surface, a tough hydrophilic layer coated over andfirmly bonded to said organophilic surface, said hydrophilic layer being liquid permeable throughout its depth, and being characterized in becoming friable upon the in situ reduction therein of metal ions to their metallic state and subsequent removal of the reduction product, and a metal-ion reduction-promoter disposed at the inner surface of said hydrophilic layer, said hydrophilic layer being stabilized against undue reduction of metal ions passing therethrough prior to contacting the reduction-promoter at said inner surface, said hydrophilic layer, upon transfer therethrough in certain areas of metallic ions tosaid inner surface and into contact with said reduction promoter to become reduced to the metallic state, being readily broken cleanly away in said areas of such transfer to lay bare the underlying organophilic surface and define a printing image, while remaining hydrophilic ,and firmly bonded in the remaining areas.
  • a sheet structure suitable for printing photolithographically, comprising a base sheet having an organophilic surface, a though hydrophilic layer coated over and firmly bonded to said organophilic surface, said hydrophilic layer being liquid permeable throughout its depth, and being characterized in becoming friable upon the in situ reduction therein of metal ions to their metallic state and subsequent removal of the reduction product, a metal-ion reduction-promoter within said hydrophilic layer adjacent the inner surface thereof, and an inhibitor dispersed insaid hydrophilic layer to inhibit undue reduction of metal ions passing therethrough prior to contacting the reduction-promoter at said inner surface, said reduction-promoter upon being contacted by metal ions transferred through the hydrophilic layer in certain areas thereof, effectively reducing the metal ions to their metallic state to rupture the bond at the interface between the hydrophilic and organophilic layers and provide easy removal of the hydrophilic layer within said certain areas to lay bare the underlying organophilic surface, thereby defining a printing plate having a printing image in said certain areas, with
  • a sheet structure suitable for printing photolithographically comprising a base sheet having an organophilic surface, a tough hydrophilic layer coated over and firmly bonded to said organophilic surface, said hydrophilic layer being liquid permeable throughout its depth, and being characterized in becoming friable upon the in situ reduction therein of metal ions to their metallic state and subsequent removal of the reduction product, said hydrophilic layer containing a metal-ion reduction promoter substantially only at the interface between said hydrophilic and organophilic layers, said reduction promoter upon being contacted by metal ions transferred through the hydrophilic layer in certain areas thereof, effectively reducing the metal-ions to their metallic state to permit rupture of the bond at the interface between the hydrophilic and organophilic layers and provide easy removal of the hydrophilic layer within said certain areas to lay bare the underlying organophilic surface, thereby defining a printing plate having a printing image in said certain areas, with the remaining areas, coated with the firmly bonded remaining areas of the hydrophilic layer, forming the background.
  • a sheet structure suitable for printing photolithographically comprising a base sheet having an organophilic silica layer coated over and firmly bonded to said organophilic surface, said silica layer being liquid permeable throughout its depth, and being characterized in becoming friable upon the in situ reduction therein of silver ions to their metallic state and subsequent removal of the reduction product, a light-sensitive high contrast photographic emulsion coating lying in contact with the silica layer, and silver reduction nuclei disposed at the inner surface of said silica layer, said silica layer being stabilized against undue reduction of silver ions passing therethrough prior to contacting the silver reduction nuclei at said inner surface and, upon processing of the sheet to expose certain areas of the photographic emulsion and to transfer silver halide from the unexposed areas thereof through the hydrophilic layer to its inner surface to there become 'reduced to silver metal, being readily broken cleanly away in said unexposed areas to lay bare the underlying organophilic surface and define a printing image, while remaining hydrophilic and firmly firmly
  • a metal of selectively imaging a substrate overcoated with a friable liquid permeable hydrophilic material comprising passing metal ions through the depth of said layer of hydrophilic material and reducing said metal ions to their metallic state at the interface of said hydrophilic layer and said substrate in certain areas, avoiding reduction of said metal ions in the remaining areas of said plate to define an image.
  • a process for printing photolithographically by utilization of a sheet structure comprising a base sheet having a conductive metal surface, an unexposed organophilic photoconductive layer that becomes electrically conductive when exposed to light coated over the metal surface of the base sheet, a tough, liquid permeable hydrophilic layer firmly bonded to the photoconductive meterial, and being characterized in becoming friable upon the in situ reduction therein of metal ions to their metallic state and subsequent removal of the reduction product, the process comprising exposing said photoconductive material to light in certain image areas, subjecting said sheet to an electromotive force in an electrolytic environment wherein said conductive metal is connected as the cathode thereby causing transfer of the metal ions of an electrolyte through the hydrophilic layer, depositing and reducing said metal ions at said interface within said image areas, and rupturing the bond at said interface removing said hydrophilic layer within said certain areas and laying bare the underlying organophilic sur face to define a printing plate having a printing image in said certain areas and
  • a sheet structure suitable for photolithographic printing comprising a base sheet having a hydrophobic surface, a nucleated hydrophilic coating overlying the non-image areas of said surface, said hydrophobic surface being exposed in the image areas, said coating being characterized by the ability to receive silver halide by diffusion transfer in image areas when an exposed negative is brought into contact with said coating in the presence of a developing solution for the negative, metallic silver being formed in said coating due to the reduction of said halide resulting from reaction with said developing solution thereby enabling the removal of said coating in said image areas.
  • a method for the formation of a sheet structure suitable for photolithographic printing comprising the steps of providing a base sheet having an ink receptive hydrophobic surface, applying a coating over said sur- 7 face comprising a nucleated hydrophilic material, said coating being characterized by the ability to receive silver halide by diffusion transfer when an exposed negative is brought into contact with said coating in the 14.
  • said coating comprises a thin, relatively porous film, and wherein the formation of metallic silver in the,
  • image areas during the developing operates to physically weaken the film in the image areas to thereby enable removal of said film from the image areas by washing of the sheet with an aqueous solution.
  • Col. 10, line 13 should read "organophilic surface, a tough hydrophilic silica layer coated” instead of “organophilic layer coated”.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US397986A 1964-09-21 1964-09-21 Diffusion transfer element and method of using same Expired - Lifetime US3914125A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US397986A US3914125A (en) 1964-09-21 1964-09-21 Diffusion transfer element and method of using same
FR31907A FR1459918A (fr) 1964-09-21 1965-09-20 Feuille lithographique et son procédé de fabrication
DE19651797524 DE1797524C3 (de) 1964-09-21 1965-09-21 Elektrolytophotographisches Aufzeichnungsmaterial und elektrolytophotographisches Verfahren zur Herstellung von Druckformen
GB38810/65A GB1129366A (en) 1964-09-21 1965-09-21 Lithographic plates and method of making such plates
DE1447968A DE1447968C3 (de) 1964-09-21 1965-09-21 Silbersalzdiffusionsverfahren zum Herstellen von lithographischen Druckformen
BE669880D BE669880A (de) 1964-09-21 1965-09-21
GB27986/68A GB1133856A (en) 1964-09-21 1965-09-21 Method of making lithographic sheets and sheets made thereby

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US397986A US3914125A (en) 1964-09-21 1964-09-21 Diffusion transfer element and method of using same

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US (1) US3914125A (de)
BE (1) BE669880A (de)
DE (1) DE1447968C3 (de)
FR (1) FR1459918A (de)
GB (2) GB1129366A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038077A (en) * 1974-04-04 1977-07-26 Polaroid Corporation Process comprising diffusion transfer silver image removal
FR2385538A1 (fr) * 1977-03-28 1978-10-27 Minnesota Mining & Mfg Plaque photolithographique
US4293625A (en) * 1977-03-28 1981-10-06 Minnesota Mining And Manufacturing Company Anchor layer in photolithographic receptor base contains oxide surface treated titanium dioxide
GB2304628A (en) * 1995-09-07 1997-03-26 Kodak Ltd Printing plate product

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453932A (en) * 1972-12-04 1976-10-27 Minnesota Mining & Mfg Lithographic plates and their preparation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2774667A (en) * 1951-07-02 1956-12-18 Polaroid Corp Photographic silver halide transfer process
US2971840A (en) * 1955-02-07 1961-02-14 Agfa Ag Process for the production of nonlaterally reversed positive copies by heat development
US3165458A (en) * 1961-09-22 1965-01-12 Minnesota Mining & Mfg Electrolytic recording sheets
US3245784A (en) * 1961-10-16 1966-04-12 Minnesota Mining & Mfg Lithographic master and process of preparation
US3385701A (en) * 1964-11-09 1968-05-28 Dick Co Ab Lithographic offset master and method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2774667A (en) * 1951-07-02 1956-12-18 Polaroid Corp Photographic silver halide transfer process
US2971840A (en) * 1955-02-07 1961-02-14 Agfa Ag Process for the production of nonlaterally reversed positive copies by heat development
US3165458A (en) * 1961-09-22 1965-01-12 Minnesota Mining & Mfg Electrolytic recording sheets
US3245784A (en) * 1961-10-16 1966-04-12 Minnesota Mining & Mfg Lithographic master and process of preparation
US3385701A (en) * 1964-11-09 1968-05-28 Dick Co Ab Lithographic offset master and method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038077A (en) * 1974-04-04 1977-07-26 Polaroid Corporation Process comprising diffusion transfer silver image removal
FR2385538A1 (fr) * 1977-03-28 1978-10-27 Minnesota Mining & Mfg Plaque photolithographique
US4293625A (en) * 1977-03-28 1981-10-06 Minnesota Mining And Manufacturing Company Anchor layer in photolithographic receptor base contains oxide surface treated titanium dioxide
GB2304628A (en) * 1995-09-07 1997-03-26 Kodak Ltd Printing plate product
GB2304628B (en) * 1995-09-07 1998-09-23 Kodak Ltd Printing plate product

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GB1133856A (en) 1968-11-20
DE1447968A1 (de) 1968-11-14
BE669880A (de) 1966-03-21
GB1129366A (en) 1968-10-02
DE1447968C3 (de) 1974-11-07
FR1459918A (fr) 1966-06-17
DE1447968B2 (de) 1974-04-11

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