US3161517A - Presensitized lithoplate with coated metal base and method of preparing same - Google Patents

Presensitized lithoplate with coated metal base and method of preparing same Download PDF

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Publication number
US3161517A
US3161517A US107657A US10765761A US3161517A US 3161517 A US3161517 A US 3161517A US 107657 A US107657 A US 107657A US 10765761 A US10765761 A US 10765761A US 3161517 A US3161517 A US 3161517A
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United States
Prior art keywords
hydrophilic
coating
water
adhesive
hydrophilic coating
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Expired - Lifetime
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US107657A
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English (en)
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Doggett Towers
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Warren SD Co
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Warren SD Co
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Publication date
Priority to NL278078D priority Critical patent/NL278078A/xx
Application filed by Warren SD Co filed Critical Warren SD Co
Priority to US107657A priority patent/US3161517A/en
Priority to GB15806/62A priority patent/GB936569A/en
Priority to DEW32152A priority patent/DE1266767B/de
Priority to FR896489A priority patent/FR1321290A/fr
Application granted granted Critical
Publication of US3161517A publication Critical patent/US3161517A/en
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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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/115—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having supports or layers with means for obtaining a screen effect or for obtaining better contact in vacuum printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/14—Dimensionally stable material

Definitions

  • planographic printing the design or image to be reproduced or printed is substantially level with the surface of the printing plate and is water-repellent and grease-receptive in nature.
  • Aqueous lithographic solution is applied to the imaged plate and wets the unimaged or blank areas, making them repellent to greasy printingink, but it does not wet the water-repellent image.
  • An inking-roller now passed over the surface of the wetted plate leaves no ink on the water-wet background areas; but it does leave ink on the imaged areas, which can thereafter print the image in reverse on any ink-receptive surface brought into contact therewith.
  • the image is usually first printed from the plate upon an offset blanket from which it is transferred to paper so that the final print is identical with the design on the plate.
  • an image may be formed on the plate by exposure of the plate to actinic radiation through a transparency or stencil or by means of lenses as in photography.
  • the preferred modern practice is to purchase plates which have already been sensitized with a photosensitive diazo compound. .Such presensitized plates when removed from the package are ready to be exposed without any preliminary treatment. After the plate is exposed to actinic radiation through a transparency, the image areas are water-repellent and grease-receptive and the diazo material on the background areas is hydrophilic and/or so soluble that it can be readily washed off by water or aqueous liquid.
  • the present invention results in a presensitized lithographic printing plate which is dimensionally stable and which possesses considerable latitude in regard to waterbalance. This is accomplished by providing a metal base with a water-absorptive surface of appreciable thickness and which comprises hydrophilic colloid material and pigment.
  • the usual hydrophilic colloids useful in planographic printing plates such as the water-soluble cellulose ethers, polyvinyl alcohol, starch adhesives, and the like do not adhere well to metal. It is found, however, that a thin layer of a particular form of anchoring matter between the metal base and the hydrophilic or water absorptive surface layer will cause the latter to adhere well to the base.
  • wash coats of certain resinous thermoplastic polymers containing carboxyl groups in their molecule are very satisfactory for this purpose. Somewhat less satisfactory, but still usable is an aqueous dispersion or solution of such resinous polymers. Such a coating will adhere strongly to metal such as aluminum sheet or foil, and at the same time the commonly used Water-dispersible hydrophilic adhesives can be made to adhere well to said resinous coating by heat sealing. From 4 to 6 grams per square meter of dry weight of the resinous polymer applied from organic solvent, or somewhat more if applied from aqueous dispersion, is normally adequate to ensure complete coverage of the metal base and to afford a secure anchorage for the hydrophilic layer subsequently deposited thereon.
  • a layer of aqueous coating composition comprising finely divided pigment and hydrophilic adhesive. Normally about 15 to 20 grams per square meter, dry weight, of such coating is a satisfactory quantity to use.
  • the hydrophilic coating is dried and heat sealed to the anchoring layer by heat. After it has dried the hydrophilic coating should be substantially insoluble in water. In some cases, it is desirable to include in the coating composition an ingredient to insure insolubilization of the coating when it has once been dried.
  • the dry hydrophilic coating is finally washed over with a solution of diazo sensitizing compound to make the finished product photosensitive.
  • diazo compound selected for use will be one which is not unduly sensitive to diffused light or light from ordinary incandescent lamps. It is of course desirable that it shall be possible to prepare and handle the plate under ordinary illumination without it being affected appreciably by such illumination. Care should be exercised during such preparation not to prolong such illumination unduly and to avoid exposure to direct sunlight or other intense actinic radiation.
  • the diazo compound used is one which becomes oleophilic and water-insoluble in the illuminated or exposed areas but remains hydrophilic and/ or water-soluble in the unexposed areas so that it may be readily washed off the surface.
  • the diazo compound used is one which is originally water-insoluble and oleophiilic but which upon exposure to actinic radiation becomes hydrophilic and is washed off by water or aqueous alkaline solution.
  • the image areas on the surface are left oleophilic and the background areas are left hydrophilic in character.
  • the image areas on the surface are left oleophilic and the background areas are left hydrophilic in character.
  • the drawing attached to and forming a part of this specification illustrates the photolithographic printing plate of this invention, wherein 1 indicates the photosensitive coating, 2 the hydrophilic coating, 3 the resinous adhesive binder coating, 4 the metal foil, 5 the adhesive layer for anchoring a reinforcing paper web, and 6 .the paper web.
  • any metal sheet material is operably possible for use.
  • aluminum sheet or foil has many obvious points of superiority over other metals. Its ready availability in foil thin enough to be easily wound into coils or rolls makes it the first choice. Actual thickness or unit weight of the aluminum sheet material is of little consequence insofar as end results are concerned. If the sheet is a thin foil of too little strength by itself it may suitably be backed-up or strengthened by being laminated or adhered to a supporting sheet of kraft paper or the like. Thus is produced a sheet of adequate strength with a surface dimensionally unaffected by water.
  • a typical sheet which has been found satisfactory consists of a sheet of hard aluminum foil 2 mils in thickness and having a weight of about 110 grams per square meter which is laminated or heat-sealed by means of an interposed sheet of half-mil polyethylene to a sheet of kraft paper having a weight of the order of 150 to 300 grams per square meter.
  • the anchoring coat applied to the metal surface serves the purpose of forming a bond between the metal and the subsequently applied hydrophilic coating layer and is particularly selected with this purpose and the problems posed thereby in mind.
  • the resinous polymer shall contain carboXyl radicals to ensure good adhesion to the metal surface.
  • Hydrophilic radicals such as carboxyl, hydroxyl, or amino radicals in the polymer are useful in promoting good adhesion to the superposed hydrophilic coating layer, and preferably the polymer should be thermoplastic to facilitate heat sealing it to the hydrophilic coating. It is found that while some resinous polymers make good anchoring coats for various hydrophilic top coats, certain other resinous polymers are more satisfactory with specific hydrophilic top-coats than with others.
  • a resinous polymer that appears to form a satisfactory anchoring layer for many hydrophilic top-coats is a tripolymer of 86 parts of vinyl chloride, 13 parts of vinyl acetate, and one part of maleic acid.
  • the layer of hydrophilic coating applied over the anchoring layer may be merely a film of hydrophilic colloid material. It is found, however, that lithographic prints made from such a layer may be somewhat lacking in definition and/or cleanliness of background. Consequently it is preferred to have the hydrophilic coating also contain mineral filler or pigment, which normally may be present in amount from a quantity roughly equal to the weight of hydrophilic colloid to a quantity about four times the weight of said hydrophilic colloid. While any mineral filler or pigment may be used which is nonreactive with the other components of the coating composition or with lithographic solutions, it is well known that non-hydrous pigments such as barium sulfate or titanium dioxide are to be preferred for use in lithographic printing surfaces.
  • water-soluble cellulosic or the like compounds are suitable for use in lithographic printing surfaces.
  • Such compounds include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethylhydroxyethyl cellulose, starch and the like. These are all usable as adhesive material to bind mineral pigment in the hydrophilic coating according to the invention,
  • Amino resinous condensates such as melamine-formaldehyde condensate are very suitable for use with the cellulosic compounds to promote insolubility thereof.
  • the hydrophilic coating should have several specific properties of particular importance in the context of photosensitized planographic masters or plates.
  • the coating should present an essentially continuous film at its surface. If the film is not continuous, the sensitizing compound is absorbed by the hydrophilic coating and this in turn results in a reduction in the quality of lithographic printing from the plate.
  • the hydrophilic surface must be capable of receiving and securely anchoring the sensitizing compound. This feature is important for the purpose of preserving the strength of adhesion of the image to the sheet during printing.
  • the coating must be hydrophilic. This is necessary for lithographic printing. Fourth, it must be water insoluble in order to prevent the lithographic fountain solution from washing it off. And fifth, the coating should not be absolutely smooth.
  • a slight graininess or matte finish is important not only for promoting adhesion of the sensitizer to the coating, but also to ensure a proper thickness of water layer covering the background areas during printing. Also the matte finish improves the intensity of the image. It will be appreciated that these features impose conflicting conditions on the problem. Thus it is difficult to obtain, at one and the same time, a film which is both continuous and grainy, and it is equally difficult to adhere hydrophilic materials to resinous polymers or metal.
  • polyvinyl alcohol Certain properties possessed by polyvinyl alcohol make that substance a preferred hydrophilic adhesive binder for the top hydrophilic coating.
  • polyvinyl alcohol appears to have more inherent flexibility than the cellulosic adhesives; so coating layers in which it is used are less liable to develop cracks than are less flexible coating layers.
  • Grades of polyvinyl alcohol which are appreciably soluble in cold water are usable as adhesive in the hydrophilic top-coat provided steps are taken to render the coating water-insoluble.
  • the addition of an amino-resin, such as a melamine-formaldehyde condensate, to a coating containing such grades of polyvinyl alcohol will render the finished coating layer adequately water-insoluble without significantly decreasing its hydrophilic properties.
  • the preferred grades of polyvinyl alcohol to use are those which are soluble in hot water but which are not readily soluble in cold water.
  • One such desirable grade is Vinol 125.
  • Very satisfactory results are given by use of a hydrophilic top-coat of about 15 grams dry weight per square meter applied in a uniform layer in the form of an aqueous composition of the following formula:
  • UP Concentrate 85 is an approximately 85% aqueous solution of a urea-formaldehyde condensate.
  • Tergitol 4 is the sodium sulfate derivative of 7- ethyl-Z-methyl-undecanol-4.
  • the hydrophilic coating made according to the preceding formula adheres well to a resinous copolymer of vinyl chloride, vinyl acetate, and maleic acid, such as Vinylite Resin VMCH.
  • a resinous layer may be deposited from solution in methyl isobutyl ketone in amount equal to about 4 grams dry weight per square meter.
  • the hydrophilic coating also adheres well to a layer of copolymer of vinyl acetate and crotonic acid, such as Gelva C3 or Lemac 541.
  • Such a layer may be deposited from solution in alcohol or from aqueous ammoniacal solution in amount equivalent to about 6 grams dry weight per square meter. When ammoniacal solutions are used the film should be well heated to ensure insolubilization of the resin by removal or" all the ammonia which may have combined therewith.
  • the sheet so made having a surface of aluminum foil bearing a layer of resinous anchoring coating and a top layer of hydrophilic coating containing hydrophilic adhesvie material and pigment can be photosensitized by application of a thin wash-coat of known diazo sensitizers in solution.
  • diazo sensitizers for negative-working plates it is known that satisfactory sensitization can be obtained by treatment with an aqueous solution of the zinc chloride double salt of the equi-molar condensation product of diazotized para-amino-diphenylamine with formaldehyde, or with an aqueous solution of the sulfonate of that product.
  • As little as 0.15 gram of the sensitizer per square meter of surface sensitized is adequate. More can be used if desired, of course.
  • the sensitized sheet is exposed to actinic radiation through a negative transparency the exposed areas become water-insoluble and somewhat oleophilic, while the unreacted matter on the unexposed areas remains water-soluble and is washed ofl before the plate is used.
  • a known sensitizer is 6- benzoyl 3 (1,2 naphthoquinone-Z-diazide-S-sulfonyl) pyrogallol.
  • This sensitizer may be applied from solution in methyl isobutyl ketone in'amount equivalent to about 0.25 gram dry weight per square meter of surface sensitized.
  • a compatible resinous material such as, for example, a cresol-formaldehyde condensate. If desired, the resin may be used in quantity 2 or 3 times as great as that of the sensitizer itself.
  • the exposed areas become sufliciently hydrophilic so that the exposed sensitized layer thereon can be washed oil with aqueous alkaline solution such as a 5% solution of trisodium phosphate in water.
  • aqueous alkaline solution such as a 5% solution of trisodium phosphate in water.
  • the unexposed image area remains oleophilic and is not removed by the alkaline wash.
  • the sensitized web material so produced is cut into sheets and covered by a light proof and moisture-proof wrapper. In such condition it can be stored for considerable periods of time without deterioration.
  • the user merely needs to remove a sheet from the package, expose it to actinic radiation, such as an arc-light, and then wash away the material on the unimaged areas.
  • the plate 1 is then ready to be used in lithographic printing.
  • the finished product has the desirable properties of the known coated paper planographic printing plates in regard to ease'of handling and using and possesses the same high degree of 'foolproofness shown by the paper plates. 'At the same time the product is not affected dimensionally by the presence of water or by changes in humidity to which it may be subjected. In other words it has the stability of a metal plate but at the same time has the tolerance of the best coated paper plates in regard to wide variations in operating conditions.
  • a method of preparing a photolithographic printing plate comprising the steps of depositing a thin anchor coating of a solvent solution of a thermoplastic carboxylated polymer adhesive onto a supporting substrate of an impervious flexible metal film; drying said thin anchor coating to remove solvent therefrom and to secure adhesion of said adhesive to said metal film; depositing a continuous and uniform hydrophilic coating of a water dispersion of a water dispersible hydrophilic adhesive and mineral pigment that upon drying yields a hydrophilic, water insoluble coating with a matte finish, the weight ratio of pigment to adhesive therein being in the range of 1 to 4 and said hydrophilic adhesive being selected from the group consisting of cellulose ethers, polyvinyl alcohols, and starches; drying said hydrophilic coating to remove the water from said water dispersion; thereafter heat sealing the thus dried hydrophilicv coating to said anchor coating; and sensitizing said hydrophilic coating with a wash solution of a photosensitive organic diazo compound.
  • a method of preparing a photolithographic printing plate comprising the steps of: depositing in the range of 4 to 6 grams per square meter (dry weight) of a thin anchor coating consisting of solvent solution of a thermoplastic adhesive onto a supporting substrate of a flexible impervious metal film reinforced on the reverse side with an adherent paper web, said thermoplastic adhesive being a flexible tripolyrner of vinyl chloride, a minor proportion of vinyl acetate and a small amount of maleic acid; drying said thin anchor coating to remove solvent therefrom and leave a smooth.
  • thermoplastic adhesive is a t'ripolymer of 86 parts by weight vinyl chloride, 13 parts vinyl acetate and one part maleic acid.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Laminated Bodies (AREA)
US107657A 1961-05-04 1961-05-04 Presensitized lithoplate with coated metal base and method of preparing same Expired - Lifetime US3161517A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL278078D NL278078A (en)) 1961-05-04
US107657A US3161517A (en) 1961-05-04 1961-05-04 Presensitized lithoplate with coated metal base and method of preparing same
GB15806/62A GB936569A (en) 1961-05-04 1962-04-25 Improvements relating to sensitised lithographic printing plates
DEW32152A DE1266767B (de) 1961-05-04 1962-04-27 Lithographische Druckplatte
FR896489A FR1321290A (fr) 1961-05-04 1962-05-04 Plaque pour impression lithographique

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US107657A US3161517A (en) 1961-05-04 1961-05-04 Presensitized lithoplate with coated metal base and method of preparing same

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US3161517A true US3161517A (en) 1964-12-15

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536490A (en) * 1964-04-28 1970-10-27 Pitney Bowes Inc Novel diazotype copying process
US3632375A (en) * 1969-11-14 1972-01-04 Scott Paper Co Plate for dry planography and method of making same
EP0036316A3 (en) * 1980-03-17 1982-02-17 Nippon Paint Company, Ltd Lithographic printing plates and supports therefor
US4483913A (en) * 1983-07-18 1984-11-20 Polychrome Corporation Planographic printing plate
US4552827A (en) * 1983-07-18 1985-11-12 Polychrome Corp. Planographic printing plate having cationic compound in interlayer
US4680250A (en) * 1982-12-06 1987-07-14 Nippon Foil Manufacturing Co., Ltd. Composite aluminum sheet for presensitized lithographic printing plate comprising a support having specified center line average roughness
US5188032A (en) * 1988-08-19 1993-02-23 Presstek, Inc. Metal-based lithographic plate constructions and methods of making same
EP0807534A1 (en) * 1996-05-14 1997-11-19 Agfa-Gevaert N.V. A flexible supported lithographic printing plate having improved dimensional stability
EP1312484A3 (en) * 2001-11-20 2004-10-20 Eastman Kodak Company Adhesion promoting polymeric materials and planographic printing elements containing them

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3469983A (en) * 1965-07-06 1969-09-30 Gaf Corp Preparation of photopolymer lithographic offset paper plates

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685511A (en) * 1952-05-03 1954-08-03 Eastman Kodak Co Metal reinforced cellulose ester photolithographic printing plates
US2692826A (en) * 1949-10-10 1954-10-26 Azoplate Corp Lithographic plates
US2760863A (en) * 1951-08-20 1956-08-28 Du Pont Photographic preparation of relief images
US2778735A (en) * 1953-05-22 1957-01-22 Warren S D Co Photo-sensitive coated paper plate for photo-lithography
US2983220A (en) * 1955-03-16 1961-05-09 Timefax Corp Electro-sensitive planographic printing plate
US3073723A (en) * 1958-10-03 1963-01-15 Lithoplate Inc Resinous coatings adapted to receive a light-sensitive layer in the production of lithographic printing plates
US3091528A (en) * 1958-08-19 1963-05-28 Chem Fab L Van Der Grinten N V Process and light-sensitive sheets for the production of pigment images by transfer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE477440C (de) * 1928-02-23 1929-06-11 Leopold Rado Druckplatte fuer Flachdruck, insbesondere Offsetdruck, bestehend aus einer biegsamenMetallbahn
DE909529C (de) * 1941-01-09 1954-04-22 William Craig Toland Flachdruckform
NL76463C (en)) * 1950-07-19

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2692826A (en) * 1949-10-10 1954-10-26 Azoplate Corp Lithographic plates
US2760863A (en) * 1951-08-20 1956-08-28 Du Pont Photographic preparation of relief images
US2685511A (en) * 1952-05-03 1954-08-03 Eastman Kodak Co Metal reinforced cellulose ester photolithographic printing plates
US2778735A (en) * 1953-05-22 1957-01-22 Warren S D Co Photo-sensitive coated paper plate for photo-lithography
US2983220A (en) * 1955-03-16 1961-05-09 Timefax Corp Electro-sensitive planographic printing plate
US3091528A (en) * 1958-08-19 1963-05-28 Chem Fab L Van Der Grinten N V Process and light-sensitive sheets for the production of pigment images by transfer
US3073723A (en) * 1958-10-03 1963-01-15 Lithoplate Inc Resinous coatings adapted to receive a light-sensitive layer in the production of lithographic printing plates

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536490A (en) * 1964-04-28 1970-10-27 Pitney Bowes Inc Novel diazotype copying process
US3632375A (en) * 1969-11-14 1972-01-04 Scott Paper Co Plate for dry planography and method of making same
EP0036316A3 (en) * 1980-03-17 1982-02-17 Nippon Paint Company, Ltd Lithographic printing plates and supports therefor
US4556462A (en) * 1980-03-17 1985-12-03 Nippon Paint Co., Ltd. Method for producing a lithographic printing plate
US4680250A (en) * 1982-12-06 1987-07-14 Nippon Foil Manufacturing Co., Ltd. Composite aluminum sheet for presensitized lithographic printing plate comprising a support having specified center line average roughness
US4483913A (en) * 1983-07-18 1984-11-20 Polychrome Corporation Planographic printing plate
US4552827A (en) * 1983-07-18 1985-11-12 Polychrome Corp. Planographic printing plate having cationic compound in interlayer
US5188032A (en) * 1988-08-19 1993-02-23 Presstek, Inc. Metal-based lithographic plate constructions and methods of making same
EP0807534A1 (en) * 1996-05-14 1997-11-19 Agfa-Gevaert N.V. A flexible supported lithographic printing plate having improved dimensional stability
EP1312484A3 (en) * 2001-11-20 2004-10-20 Eastman Kodak Company Adhesion promoting polymeric materials and planographic printing elements containing them

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DE1266767B (de) 1968-04-25
NL278078A (en))
GB936569A (en) 1963-09-11

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