US2714066A - Planographic printing plate - Google Patents

Planographic printing plate Download PDF

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US2714066A
US2714066A US519900A US51990055A US2714066A US 2714066 A US2714066 A US 2714066A US 519900 A US519900 A US 519900A US 51990055 A US51990055 A US 51990055A US 2714066 A US2714066 A US 2714066A
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Prior art keywords
plate
light
silicate
film
sensitive
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US519900A
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English (en)
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Clifford L Jewett
John M Case
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority to BE540601D priority Critical patent/BE540601A/xx
Priority to BE507657D priority patent/BE507657A/xx
Priority to GB27413/51A priority patent/GB718525A/en
Priority to DEM11920A priority patent/DE907147C/de
Priority to FR1051461D priority patent/FR1051461A/fr
Priority to CH309940D priority patent/CH309940A/de
Priority to US519900A priority patent/US2714066A/en
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US523951A priority patent/US3136636A/en
Publication of US2714066A publication Critical patent/US2714066A/en
Application granted granted Critical
Priority to FR69770D priority patent/FR69770E/fr
Priority to DEM27983A priority patent/DE1091433B/de
Priority to CH357974D priority patent/CH357974A/de
Priority to GB23641/55A priority patent/GB815471A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • B41N3/038—Treatment with a chromium compound, a silicon compound, a phophorus compound or a compound of a metal of group IVB; Hydrophilic coatings obtained by hydrolysis of organometallic compounds
    • 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
    • G03F7/016—Diazonium salts or compounds
    • G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders

Definitions

  • PLANOGRAPHIC PRINTING PLATE Original Filed Aug. 16, 1954 LIGHT-5EN5ITIVE DIAZO RESIN SILICATE TREATMENT ALUMINUM SHEET 10 /j-* ALUMINUM SHEET SILICATE TREATMENT COATING of IMAGE DEVELOPER LIGHTREACTED DIAZO RESIN SILICATE TREATMENT ALUMINUM SHEET INVENTORS CLIFFORD LJEWETT JOHN M. CASE w mmf ATTORNE 5 LIGI-IT-REACTED DIAZO RESIN United States Patent i PLANOGRAPHEC PRINTING PLATE Cliliord L. .lewett, Minneapolis, and John M. Case,
  • This invention relates to planographic printing plates. it particularly concerns plates of a type which may be used on well known commercial forms of lithographic presses.
  • This application is a continuationdn-part of our copending application Serial No. 199,5 66, filed December 6, 1950, and is a division of our application Serial No. 1:
  • Our invention is especially concerned with a plate formed from a thin metal sheet having at least one surface thereof reated to provide a tightly bonded, thin, preferably inorganic, hydrophilic surface formed from a solution of an alkali metal silicate, silicic acid, or other treating agent which will form a permanently hydrophillc scum-preventing and tone-reducing film overlying and in firmly-bonded contact with the surface of the plate, and having a coatin of light-sensitive organic material such as a light-sensitive diazo resin or other light-sensitive organic nitrogen-containing material over the exposed hydrophilic treated surface, i. e. over the exposed surface of the scum-preventing and tonereducing film or treatment.
  • a light-sensitive organic material such as a light-sensitive diazo resin or other light-sensitive organic nitrogen-containing material
  • Lithographic plates of one type and another have been known for a great many years; for example, see Stevens, U. S. Patent No. 556,380, granted March 17, 1896, which is one of the early patents connected generally with this subject.
  • Zahn U. S. Patent No. 2,100,063, granted November 23, 1937; and Toland et al., U. S. Patent No. 2,373,357, granted April 10, 1945, are examples from a large number of other patents which describe various forms of lithographic plates, and which have been granted since the aforesaid Stevens patent.
  • the lithographic plates employed in commerce and industry have consisted mainly of grained zinc plates, commonly produced by people who are in the business of graining plates. These grained plates are customarily supplied to a large number of shops throughout the country that make finished plates for the printer and lithographer.
  • planographic plates which are presensitized, i. e. are ready for an exposure through a negative or stencil without further treatment. These plates can be stored for considerable periods of time, i. e. weeks or months, and still be used, merely upon exposure to light through a negative or stencil, followed by washing off the unexposed light-sensitive material.
  • German Patent No. 581,697 which is equivalent to Schmidt and Zahn U. S. Patent No. 2,063,631, granted December 8, 1936; and Stevens, U. S. Patent No. 556,380, granted March 17, 1896.
  • Light-sensitive diazo resins and other like light-sensitive organic materials are notably sensitive to metals.
  • Kalle British Patent No. 699,413, published November 4, 1953, at page 1 points out that if water soluble diazo compounds, or like light-sensitive substances, are coated on metal supports, a plate which can be stored in the unexposed state, i. e. a presensitized plate, cannot be made, owing to the decomposition of the light-sensitive substance caused by the metal.
  • Others concerned with metal plates have coated them with a substantial layer of cellulose acetate, or other material, and then hydrolyzed the surface of the acetate and coated the diazo resin or equivalent thereover.
  • -' is also an object of our invention to provide a presensiitized plate which can replace the prior art method, cumbersorhe under many circumstances, of securing grained 'Zinc plates and then subsequently coating the same with V a light-sensitive colloidal coating.
  • a further object is to provide a presensitized plate which preferably is free of surface roughness or grain, and from which sharp lined impressions can be produced and from which printing of high resolution, that is, extreme clarity of detail of the printed matter, can be obtained.
  • a further object is to provide a presensitized lithographic plate of high dimensional stability which will be suitable for applications where accurate registration is required such, for example, as in multicolor work, where the same sheet is successively printed from different lithographic plates.
  • Another object is to provide, for the first time, a commercially acceptable presensitized lithographic plate.
  • Fig. 1 shows an aluminum sheet 10, in broken-away view, showing a scum-preventing film or thin silicate treatment 11 tightly and. chemically bonded to one surface of the aluminum sheet 10;
  • Fig. '2- is like Fig. 1 but additionally has a thin coating 12 of a water-soluble light sensitive diazo resin coated over or absorbed by the said silicate coating;
  • Fig. 3 is like Fig. 2 except the plate of Fig. 2 has .been exposed to ultraviolet light through a photographic negative and then washed with water or standard gum arabic fountain solution, leaving the hydrophobic and organophilic diazo image 12a; and
  • Fig. 4 is like Fig. 3 except that the exposed plate of Fig. 3 has its image surface wiped with an image developer, leaving an extremely thin coating of image developer 13.
  • the aluminum sheet 10 though being a foil having a thickness of only about .005 to .012 inch, is shown in broken-away view, in respect to its thickness as well as its length, to illustrate the fact that the silicate treatment 11 is really very thin compared with the aluminum foil 10.
  • the silicate treatment is probably little more than -a monomolecular layer.
  • diazo light-sensitive resin 12 is shown in the drawing as also being a very thin coating, but it is not the intention in the drawing to illustrate whether the light-sensitive diazo resin coating is equal to, greater than, or less than the thickness of the silicate treatment. Actually, the diazo coating is apparently absorbed to some extent in the surface of the thin silicate treatment.
  • a salient embodiment of our invention consists in providing a thin treatment or film, probably often substantially of monomolecular thickness, of a hydrophilic inorganic material (e. g. formed from treatment with an alkali metal silicate solution) on a surface of a given metal plate, for example, an aluminum plate.
  • a hydrophilic inorganic material e. g. formed from treatment with an alkali metal silicate solution
  • the aluminum plate may be from .005 to .012 inch in thickness, although this obviously depends upon the type of press on which the plate is to be employed and other factors, and these dimensions may be greatly varied as circumstances permit.
  • a thin coating of preferably a water-soluble lightsensitive diazo resin Over the exposed silicate treated or like hydrophilic and scum-preventing surface, we apply a thin coating of preferably a water-soluble lightsensitive diazo resin.
  • This product following drying, may be packaged in any convenient ligh -proof container, and shipped to the customer in a distant city or State.
  • the customer desires to use the plate, which may be many weeks, or even months, after the plate was manufactured and shipped to him, he will remove the plate from its package under subdued light, place it in contact with a negative or stencil, then expose it to a source of ultraviolet light for a short period of time, e. g. from 1 to 5 minutes, depending upon the intensity of the ultraviolet light, and then wash the surface of the plate with Water, whereupon the unexposed diazo material (that shielded by the stencil or negative), which remains water-soluble, is cleanly washed off, leaving the hydrophilic silicate treated surface exposed in those areas.
  • the portion of the diazo coating which was exposed to the ultraviolet light was thereby insolubilized and rendered hydrophobic and organophilic (that is, water-repellent and ink-receptive), expelling nitrogen from the molecule in the process.
  • the diazo light-sensitive material it becomes very strongly bonded to the surface of the scumpreventing film, which is usually an inorganic material such as a silicate.
  • This plate is then ready to be placed on a lithographic press, without further treatment, and used in printing or reproducing the desired writings or images.
  • the image developer may take various forms.
  • One example is a pigmented resin emulsion which will adhere to the inkreceptive areas but will not adhere to the hydrophilic areas of the plate.
  • a printers developing ink can also be 'used'as an image developer.
  • An example of an image developer, which we have found to be particularly useful, is described in a copending application of Myron W.
  • the image developer is of this practical importance: prior to the application of the image developer, the image is not visible. If a plate in that form is presented to the lithographer or printer, he cannot be sure whether he is putting the plate on the press correctly or whether he has it backwards. Additionally, in the absence of the visible image, the ressman would not know whether he had an exposed plate, unless this were denoted by some coding system or such like. In addition to making the image visible, so the pressman can see it, a good image developer also (a) helps the plate to ink up more readily when placed on the press, and (b) strengthens the image so that more copies can be run from a single plate, while still getting clear reproductions.
  • Example Aluminum foil or sheet material of about .005 inch in thickness is first made ready for treatment with a silicate. Since greasy lubricants are commonly used in aluminum mills during the rolling operation, it is first desirable to treat the aluminum foil or sheet so as to remove any greasy film, so that the surface exposed will be an aluminum surface.
  • One method which we have found to be advantageous in cleaning the aluminum surface is to immerse the same in a solution of trisodium phosphate for a sufiicient time only to clean the aluminum, e. g. for a period of 5 minutes.
  • the temperature of the solution may be controlled at approximately 160 F.
  • nitric acid of about concentration, employed at room temperatures, will clean the scum off of the surfaces of the aluminum foil or sheet material and leave it in good condition for the subsequent steps of our plate making operation.
  • nitric acid of about concentration, employed at room temperatures, will clean the scum off of the surfaces of the aluminum foil or sheet material and leave it in good condition for the subsequent steps of our plate making operation.
  • Al foil or sheet material is thoroughly rinsed with water to remove any residual acid.
  • the cleaned surface of the aluminum is then treated with a solution of an alkali metal silicate, calcium silicate, silicic acid, colloidal hydrated silica or polymerized silicic acid (such as Du Ponts Ludox), or equivalent,
  • a suitable type of sodium silicate can be chosen from those commercially available having a silica to soda ratio within the range from 3.2 to 1 to 1.8 to 1; and a particularly suitable one is Star Brand, of Philadelphia Quartz Company, having a silica to soda ratio of 2.50 to l.
  • the concentration of the sodium silicate in the solution may advantageously be about 2 to 5%, e. g. 2%, although weaker or stronger solutions can be employed.
  • Calcium silicate and silicic acid are relatively insoluble in water (less than one percent) and are commonly described as being insoluble in water. Insolubility, however, it is not total, a saturated solution of each containing probably in excess of .01 of one percent of the respective chemicals in solution. Regardless of the concentration achieved, saturated solutions of calcium silicate and silicic acid are sufficient usefully to treat an aluminum sheet prior to applying a light-sensitive diazo resin or equivalent, to make our plates.
  • magnesium silicate, copper silicate and aluminum silicate illustrate materials having such a high degree of insolubility as to be useless in the practice of our invention.
  • silicic acid in solution, diluted with water to a concentration range of 1 percent to .1 percent Ludox, has been found to be a fully satisfactory equivalent of sodium silicate for our purposes, even though du Pont trade literature states that This product should not be considered as an alkali silicate, such as the sodium silicate of commerce, because in contrast to sodium silicate, it contains no significant quantity of alkali and in general Ludox as few properties in common with alkali silicates.
  • the colloidal water dispersion of silica sold by Monsanto Chemical Co. under the trade name of Syton-W-ZO" and commonly known as a silica sol disclosed by Jahoda in his U. S. Patent No.
  • a preferred method of treating the aluminum foil or sheet material with the soluble silicate involves dipping a cleaned aluminum surface in the silicate solution maintained at temperatures of the order of 21'2 F. This can conveniently be done by running a web of aluminum foil continuously through an immersion bath. At these temperatures the soluble silicate will react with the surface of the aluminum to form an insoluble hydrophilic silicious surface. After this treatment, the excess soluble silicate, and any other soluble materials present, are immediately thoroughly washed away, and the treated foil or sheet is dried. The resulting silicate treatment on the surface of the aluminum foil or sheet is extremely thin but is very abrasion resistant. It is also substantially free of water-soluble material.
  • the silicate treatment is very effective in rendering the surface of the aluminum permanently hydrophilic: the aluminum sheet in this form will not oxidize to a hydrophobic surface on exposure to air, as it will do in the absence of such a silicate treated surface or equivalent.
  • the silicate treatment or equivalent provides a permanently hydrophilic scum-preventing and tone-reducing film or treatment.
  • the silicate treated aluminum foil or sheet ust described is of quite a smooth character and usually has a metallic sheen or relatively smooth appearance,as contrasted Withthe dull appearance of various prior art grained plates. While some very slight amount of etching may unavoidably occur on the aluminum surface of the sheet during the cleaning operation, this is so small that it does not impart to the finished silicate treated sheet a rou h surface or a matte appearance. This is important in securing the highest performance characteristics, sought after in our finished presensitized lithographic plates, particularly where fine line work or fine half-tones are being reproduced.
  • the smooth silicate treated surface of our plate for example produced as just described, without graining or deep etching, has the property of tenaciously holding image formed by exposure to light of light-sensitive organic nitrogen-containing material, e. g. light-sensitive diazo compounds, on the surface thereof, as described and illustrated hereinbelow.
  • light-sensitive organic nitrogen-containing material e. g. light-sensitive diazo compounds
  • Suitable light-sensitive diazo resins are available commercially, from several manufacturers, e. g. Ringwood Chemi- I? cals, Inc. (formerly Edwal Laboratories, Inc.), Ringwood, Illinois.
  • One suitable method of making a suitable light-sensitive diazo resin is as follows: thirty-four parts of the sulfate salt of para-diazodiphenyl amine (available, for example, from the Fairmount Chemical Company, Newark, N. 1., at the present time as Para-diazodiphenyl amine salt) is mixed with 3.25 parts of para-formaldehyde and 4.5 parts of anhydrous zinc chloride. The above mixture is gradually introduced into 135 parts of cool sulfuric acid of 66 Baume, care being taken that the temperature does not exceed 6 C.
  • the brown solution decomposes to a black tarry material, essentially an impure diazo resin, which is removed and dissolvedin water.
  • Addition of an excess of a saturated zinc chloride solution to this aqueous diazo resin solution precipitates a yellow solid which is removed; this yellow solid is then further purified by dissolving in water and precipitating by the addition of alcohol.
  • This new precipitate is the purified light-sensitive diazo resin and, in the form of a dilute solution in water, for example, about a 1% solution, is used in applying a light-sensitive coating to our aluminum sheet or the like, above described, which has been given a silicate treatment or otherwise provided with a scum-preventing and tone-reducing film overlying and in contact with the surface of the metal, as herein illustrated.
  • the reactions and precipitations employed in the mak- I ing of the light-sensitive diazo resin are carried out under subdued light, for example, under a yellow light. This is also true of the operation of coating the silicate or like inorganic or other hydrophilic surface of the aluminum sheet with a dilute solution of the light-sensitive diazo resin or equivalent.
  • the dilute solution of light-sensitive diazo resin may be applied to the exposed surface of the permanently hydrophilic silicate treated sheet, or equivalent, above described, by a roll coating method, for example.
  • the diazo coating be an extremely thin one, for example, leaving a residue of about 0.903 gram, or even less, e. g. 0.001 gram, of the diazo resin per square foot of plate area.
  • a heavier residue of diazo resin but still a thin film, can be coated on the surface.
  • the treated and sensitized sheet is then die cut to standard plate sizes and, continuing under subdued light, the plates are packaged in light-tight packages, in which they are sent to the users and customers.
  • the customer in using the same, removes them from the package under subdued light and places a negative or sten cil thereover and exposes the same to ultraviolet light, to produce the desired image, as already described hereinabove.
  • Sensitized plates made according to our above described method are more sensitive to light than conventional albumin, ammonium bichromate plates; and our plates can be sufficiently exposed in about two-thirds the time.
  • Exposure of our presensitized lithographic plates may be carried out in a printing frame under a source of ultraviolet light. Carbon arcs may be used but are not required. Photo-flood bulbs and black light fluorescent tubes will also give satisfactory results. While the exposure time is not critical, under-exposure may result in broken images or no image at all. Extreme over-exposure may cause dirty highlights and blocked-up shadows in half-tone areas. While the user of our presensitized plates has considerable latitude in the amount of exposure, the foregoing will serve to guide him from undue extremes of over-exposure or under-exposure.
  • the plate where a diazo resin is used as the sensitizer
  • a solution of gum arabic which dissolves and removes the unreacted diazo sensitizer.
  • the image is invisible. While the plate is still Wet with the gum arabic solution, an image developer or strengthener consisting of a resin emulsion (or, alternatively, a printers developing ink of conventional type) is poured on the plate and rubbed in quickly with a soft pad or cotton wad. The excess image developer should be wiped away before it dries completely.
  • the resinous portion of the image developer should preferably contain a pigment or dye which will make the image clearly visible as the particles of resin adhere to the hydrophobic and organophilic image.
  • the plate is then ready for the press, or it may be coated with gum arabic if it is to be stored before use.
  • lithographic plates are of such nature, due to the particular materials and the thickness thereof, that they do not wrinkle or stretch during processing or on the press (as do paper or plastic planographic plates, for example) and, therefore, are particularly suitable for 1 9 lithographic printing, even where very accurate registration is required.
  • Aluminum foil to be used for our process is one produced by the Aluminum Company of America and designated as 381-119, the same containing about 1.25% manganese alloyed with the aluminum.
  • Aluminum foil or sheeting which would be too soft and pliable to be well suited for our use if employed in the form of relatively thin gauge sheets, although any commercial type of aluminum which is stifl enough to resist wrinkling and creasing, in the form of thin sheets or foil, may be employed.
  • water-soluble or water-dispersible silicates of commerce are the most desirable and convenient materials for producing permanently hydrophilic surface treatments on metal sheets for our purposes, yet with variations in metal sheets and/or with variations in the light-sensitive organic material to be employed and/or with variations in the treating procedure, treating materials other than the water-soluble silicates may be useful or even preferred.
  • silicon-containing compounds such as Ludox colloidal silica or saturated solutions of calcium silicate have been employed by us, experimentally, as treating materials, because of special characteristics of these solutions, such as stability, lower alkalinity and others.
  • Certain non-silicon compounds e. g. certain polyhydroxy and polymolecular organic acids have also been experimented with, which render metal surfaces permanently hydrophilic and of a scum-preventing nature, and provide a strong bond between the metal surfaces above described and light-reacted diazo resin or the like. Further information on this matter will be made the subject of a separate application.
  • Diazo materials especially diazo resins, have been described herein as the preferred light-sensitive materials for our purposes. However, variations in this regard are contemplated.
  • the azide of our preferred diazo resin can, with suitable modifications, be used as the light-sensitive coating.
  • This polymeric azido resin is not water soluble and only slightly soluble in common organic solvents, but a concentration suitable for coating can be obtained using as solvents toluene or methyl cellosolve, or mixtures of these, or other organic solvents.
  • the un-light-decomposed azide can conveniently be re moved by a water-toluene mixture, leaving a hydrophobic printing image of water-insoluble, light-reacted azide.
  • Simons describes a paper lithographic plate in which silica, freshly precipitated from sodium silicate, is used to form, a grained printing surface.
  • Champion et al. describe a direct image printing plate in which the margins only are coated with sodium silicate to provide a smudgeproof border.
  • Ayers employs sodium silicate, said to serve as a protective coating, over the printing face of an exposed albuminbichrornate coated zinc plate.
  • Toland et a1. provide a rough, grained surface on paper-backed lithographic plates by applying to the paper a mixture of clay, calcium carbonate or silica, bonded together with sodium silicate, as a base for an albumin typelightsensitive coating.
  • Mason provides a method for the multiple etching of aluminum to produce matte surfaces, and may employ sodium fluoride and sodium silicate in his operation.
  • none of these patents or publications disclose a presensitized plate of any type.
  • our invention concerns, not merely a presensitized plate, but a presensitized plate in which a metal surface, preferably a smooth metal surface, e. g. aluminum, is provided with a permanently hydrophilic thin film or surface treatment, preferably formed from an aqueous sodium silicate solution or equivalent and chemically bonded to the metal surface; and having applied to the silicate, or other permanently hydrophilic surface or scum-preventing and tone-reducing film, a thin coating of a light-sensitive diazo resin, or other light-sensitive organic material which, upon exposure to light, will tightly and preferably chemically bond itself to the silicate or other permanently hydrophilic surface.
  • Our presensitized planographic plate of the construction just summarized, and hereinabove illustrated, provides a new article for commerce and industry. It is a plate which will yield high quality reproductions and long plate life, as well as fulfilling other objectives above set forth.
  • our plates can be used to advantage in the photographic preparation of permanent metal name plates, instruction panels, templates, Wiring diagrams, dial and scale faces, advertising specialties, signs, maps and the like.
  • the plate is exposed to ultra-violet light through a photographic negative, followed by desensitizing and inking or de veloping as described above.
  • the visible image may be produced by the use of an ordinary lithographic printing ink'or an image developer, such, for example, as that disclosed above and also described in detail in the co pending application of Myron Hall, Serial No. 239,841.
  • the developed plate with its visible image After the developed plate with its visible image has been washed and dried, it may be used as such, or the surface may be further protected by spraying with a clear lacquer.
  • Such plates may be fastened to machinery and the like, and made a permanent part thereof, to aid in the operation and maintenance of the machinery, and to identify its parts, its manufacturer, etc. This use of our invention is becoming of increased importance.
  • said metal sheet having on at least one surface thereof a permanently hydrophilic scum-preventing and tone-reducing film formed by reacting an aqueous solution of a soluble silicate with the surface of said metal sheet, said film overlying and being firmly bonded to said surface of said sheet and being substantially free of water-soluble material, said film being further characterized in that it will cause an in situ insolubilized diazo image strongly to adhere to the surface of the sheet, and over and in contact with said film a thin coating of a light-sensitive diazo resin, said light-sensitive material being characterized in that, upon exposure of the plate to ultra-violet light through a stencil or negative, it will react in the exposed portions, expelling nitrogen from the molecule and forming a water-insoluble hydrophobic and organophilic material which is tightly bonded to said permanently hydrophilic film, providing a printing image, the light-sensitive resin material being readily washed away from the unexposed areas, leaving the permanently hydrophilic film
  • a presensitized planographic plate comprising an aluminum sheet having at least one smooth surface thereof rendered permanently hydrophilic by treatment with an aqueous solution of an alkali metal silicate, said permanently hydrophilic surface being provided by a thin layer of the reaction product of said aluminum and said silicate and being substantially free of water-soluble materials, said permanently hydrophilic surface being coated with a thin coating of a water-soluble light-sensitive diazo resin, said diazo resin being characterized in that, upon exposure of the plate to ultra-violet light through a stencil or negative, it will react in the exposed portions to form an image of water-insoluble, hydrophobic and organophilic material which is tightly bonded to said permanently hydrophilic surface, the diazo resin remaining water-soluble and capable of being readily washed away clean from the unexposed areas, leaving said permanently hydrophilic surface bare in said areas.
  • a plate suitable for use in planographic printing and related uses comprising an aluminum sheet having on at least one surface thereof an extremely thin layer of the reaction product of said aluminum sheet and an aqueous solution of an alkali metal silicate, providing a permanently hydrophilic surface, said surface being substantially free of water-soluble materials, and said surface having thereover a thin coating of a water-soluble light-sensitive diazo resin, which, upon exposure of the plate to ultra-violet light through a stencil or negative, will react in the exposed portions to form an image of water-insoluble, hydrophobic and organophilic material which is tightly bonded to said permanently hydrophilic surface.
  • a plate suitable for use in planographic printing and related uses comprising a sheet having as at least one surface thereof a metal from the class consisting of aluminum, zinc and tin, and over and bonded to the surface of said metal an extremely thin layer of the reaction product of said metal and an aqueous solution or 13 an alkali metal silicate, providing a permanently hydrophilic surface thereon, said surface being substantially free of water-soluble materials, and said surface having coated thereover a thin coating of a Water-soluble lightsensitive diazo resin.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US519900A 1950-12-06 1955-07-05 Planographic printing plate Expired - Lifetime US2714066A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
BE540601D BE540601A (sk) 1950-12-06
BE507657D BE507657A (sk) 1950-12-06
GB27413/51A GB718525A (en) 1950-12-06 1951-11-22 Improvements in or relating to photographically presensitized metal plates
DEM11920A DE907147C (de) 1950-12-06 1951-12-01 Vorsensibilisierte Flachdruckplatte
FR1051461D FR1051461A (fr) 1950-12-06 1951-12-03 Planches d'impression planographique présensibilisées
CH309940D CH309940A (de) 1950-12-06 1951-12-06 Verfahren zur Herstellung einer vorsensibilisierten planographischen Platte und nach diesem Verfahren erhaltene Platte.
US519900A US2714066A (en) 1950-12-06 1955-07-05 Planographic printing plate
US523951A US3136636A (en) 1950-12-06 1955-07-25 Planographic printing plate comprising a polyacid organic intermediate layer
FR69770D FR69770E (fr) 1950-12-06 1955-08-13 Planches d'impression planographique présensibilisées
DEM27983A DE1091433B (de) 1950-12-06 1955-08-15 Vorsensibilisierte Flachdruckplatte
CH357974D CH357974A (de) 1950-12-06 1955-08-15 Verfahren zur Herstellung einer vorsensibilisierten, für den Flachdruck verwendbaren Platte
GB23641/55A GB815471A (en) 1950-12-06 1955-08-16 Improved photosensitized planographic metal plates

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US19956650A 1950-12-06 1950-12-06
US45014954A 1954-08-16 1954-08-16
US519900A US2714066A (en) 1950-12-06 1955-07-05 Planographic printing plate
US523951A US3136636A (en) 1950-12-06 1955-07-25 Planographic printing plate comprising a polyacid organic intermediate layer

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WO2020158288A1 (ja) 2019-01-31 2020-08-06 富士フイルム株式会社 平版印刷版原版、平版印刷版の作製方法、及び、平版印刷方法
WO2020158287A1 (ja) 2019-01-31 2020-08-06 富士フイルム株式会社 平版印刷版原版、平版印刷版の作製方法、及び、平版印刷方法
WO2020262692A1 (ja) 2019-06-28 2020-12-30 富士フイルム株式会社 機上現像型平版印刷版原版、平版印刷版の作製方法、及び、平版印刷方法
WO2020262691A1 (ja) 2019-06-28 2020-12-30 富士フイルム株式会社 機上現像型平版印刷版原版、平版印刷版の作製方法、及び、平版印刷方法
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WO2021132647A1 (ja) 2019-12-27 2021-07-01 富士フイルム株式会社 平版印刷版原版、平版印刷版の製造方法および印刷方法
WO2022138880A1 (ja) 2020-12-25 2022-06-30 富士フイルム株式会社 ネガ型平版印刷版原版の積層体、及びネガ型平版印刷版の作製方法
WO2022138710A1 (ja) 2020-12-25 2022-06-30 富士フイルム株式会社 平版印刷版原版、平版印刷版の製造方法、印刷方法、アルミニウム支持体の製造方法
WO2023032868A1 (ja) 2021-08-31 2023-03-09 富士フイルム株式会社 機上現像型平版印刷版原版、及び印刷版の作製方法
WO2023032992A1 (ja) 2021-08-31 2023-03-09 富士フイルム株式会社 平版印刷版用支持体、平版印刷版原版、平版印刷版の製造方法
WO2023145972A1 (ja) 2022-01-31 2023-08-03 富士フイルム株式会社 機上現像型平版印刷版原版、平版印刷版の作製方法、平版印刷方法、及び、積層体
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EP4360880A1 (en) 2022-10-25 2024-05-01 FUJIFILM Corporation Lithographic printing plate precursor, method of preparing a lithographic printing plate, and lithographic printing method

Also Published As

Publication number Publication date
FR69770E (fr) 1958-12-30
DE1091433B (de) 1960-10-20
CH357974A (de) 1961-10-31
GB815471A (en) 1959-06-24
DE907147C (de) 1954-03-22
US3136636A (en) 1964-06-09
FR1051461A (fr) 1954-01-15
BE507657A (sk)
GB718525A (en) 1954-11-17
CH309940A (de) 1955-09-30
BE540601A (sk)

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