US3417055A - Process for preparation and separation of light sensitive stabilized diazo resins - Google Patents

Process for preparation and separation of light sensitive stabilized diazo resins Download PDF

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Publication number
US3417055A
US3417055A US648036A US64803667A US3417055A US 3417055 A US3417055 A US 3417055A US 648036 A US648036 A US 648036A US 64803667 A US64803667 A US 64803667A US 3417055 A US3417055 A US 3417055A
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Prior art keywords
resin
diazo
salt
acid
light
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Expired - Lifetime
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US648036A
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English (en)
Inventor
James F Houle
Gilden R Van Norman
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US347931A external-priority patent/US3342601A/en
Priority to DEE28725A priority Critical patent/DE1299661B/de
Priority to NL6502350A priority patent/NL6502350A/xx
Priority to BE660255A priority patent/BE660255A/xx
Priority to CH267065A priority patent/CH435335A/fr
Priority to GB38572/67A priority patent/GB1108560A/en
Priority to NO156951A priority patent/NO115071B/no
Priority to GB8295/65A priority patent/GB1108559A/en
Priority to DK103065AA priority patent/DK124245B/da
Priority to SE2495/65A priority patent/SE315909B/xx
Priority to US505041A priority patent/US3486450A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US648036A priority patent/US3417055A/en
Priority to US658559A priority patent/US3419406A/en
Priority to NO16987267A priority patent/NO124113B/no
Priority to SE8622/68A priority patent/SE320385B/xx
Publication of US3417055A publication Critical patent/US3417055A/en
Application granted granted Critical
Priority to US871607A priority patent/US3694251A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06—Amines
    • C08G12/08—Amines aromatic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy 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
    • 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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives

Definitions

  • ABSTRACT OF THE DISCLOSURE Stabilized diazo compositions for use in preparing lithographic printing plates are described.
  • the compositions are particularly useful for coating on hydrophilic layers containing certain titanium complexes.
  • This invention relates to lithographic printing plates, more particularly to offset printing plates commonly used in the lithographic trade.
  • Lithographic plates are well known in the graphic arts field, particularly those having metal supports such as aluminum or zinc.
  • aluminum has been particularly attractive for lithographic plates due to its cost, availability and light weight.
  • certain inherent disadvantages must first be overcome. For instance, it has been established that the naturally occurring oxide film on aluminum is not sufficiently hydrophilic to provide trouble-free operation on a lithographic printing press. The bare aluminum is prone to become slightly hydrophobic or oleophilic resulting in a gradual buildup of ink on the non-printing areas. This phenomena is referred to in the trade as toning or scumming.
  • toning or scumming This phenomena is referred to in the trade as toning or scumming.
  • Another method of providing an aluminum plate having an insoluble, hydrophilic layer which also isolates the diazo light-sensitive coating from the aluminum substrate is to deposit a coating on the aluminum of a silicate containing the SiO radical.
  • Such a plate has limited press life and also is subject to decreases in contrast during storage. It has been desirable to provide a plate having greater press latitude, longer press life and longer shelf life than provided by the plates of the prior art. To achieve improved characteristics for a presensitized plate, it is desirable to obtain a plate having a grained surface, an improved method of treatment to provide a hydrophilic surface, and a stabilized light-sensitive coating thereon, thus giving a combination of superior printing and keeping qualities.
  • One object of this invention is to provide hydrophilic lithographic printing surfaces. Another object is to provide a presensitized lithographic printing plate. A further object is to provide a diazo sensitized, grained aluminum, lithographic printing plate. A further object is to provide a method for the preparation of stabilized, presensitized Patented Dec. 17, 1968 "ice diazo resins. Other objects will be apparent from the following disclosure.
  • a stabilized, light-sensitive diazo resin which has been isolated from strong acid by: (1) treating the resin solution with a cadmium salt to form a mixture cadmium salt of the resin in the strong acid and (2) subsequently treating the resulting resinous salt-acid mixture with a soluble salt, the cation of which will precipitate with any undesirable acid anion; on a lithographic support, especially a grained aluminum lithographic printing plate which has been treated with a substantially water soluble titanium compound.
  • a useful source of the titanium compound for treatment of the plate support is the titanium ortho-esters such as, for example, the tetraalkyl titanates.
  • the preferred tetraalkyl titanates are those having alkyl groups with 2 to 5 carbon atoms such as, for example, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetraamyl titanate, etc.
  • the acidic constituent which is useful for reacting with the titanate produces a water-soluble titanium complex in an acid media.
  • Useful acidic constituents include, for example, fluosilicic acid, hydrofluoric acid, phosphoric acid, fluoboric acid, etc.
  • the composition for the titanium compound treatment is preferably prepared by adding the alkyl titanate which immediately reacts to form hydrous titanium dioxide which subsequently dissolves and/or reacts forming a so-called basic titanium salt. Further details of the treatment and compositions therefore are found in US. application Ser. No. 347,931 mentioned above.
  • the light-sensitive coating may be a suitably stabilized water-soluble resin containing the diazonium group which upon exposure to ultraviolet light forms an oleophilic surface or image.
  • the light-sensitive coating may be of the general Where X is chlorine;
  • M is a di or trivalent metal of the groups known to stabilize the diazonium groups, e.g. cadmium, zinc, bismuth, arsenic, antimony, tin, iron, platinum, mercury;
  • X is an anion or mixture of anions consisting of halogen or sulfates
  • Z may be a phenyl or substituted phenyl in which case the resin is an aldehyde condensation product of a p-diazodiphenylamine salt.
  • Y ' is hydrogen.
  • Z and Y may also be organic radicals functionally capable of entering into an addition polymerization, polyesterification, condensation or other reaction capable of producing a relative low molecular weight resin or capable of reacting with a preformed polymer.
  • Z and Y in this case may be the same or different, the parent diazonium compound being a substituted p-diazo aniline.
  • reactive groups are hydroxyl as in N ethyl N ([3 hydroxyethyl)-anilino, 4-diazo salts capable of reacting with polymerizable groups such as acryloyl, methacryloyl, etc.
  • the placement of various groups on the anilino nitrogen can result in the preparation of polyesters, polyethers, polyurethanes, polyacetals, polycarbonzates, etc., by direct polymerization or condensation with functionally proper preformed polymers.
  • the light-sensitive coating consists of an aldehyde condensation product of a p-diazo diphenyl amine.
  • Light-sensitive aldehyde condensation products of p-diazo diphenyl amine stabilized with metal salts are well known in the art as described in US. Patent 2,714,066.
  • Such resins are also available commercially, e.g., Diazo Resin No. 4. This material is described as a diazonium sulfate-zinc chloride double salt.
  • aluminum reacts with the diazo resin causing decomposition.
  • a suitable-resin is prepared by mixing a diazoaniline salt and an aldehyde together thoroughly in the dry state, adding the resultant mixture in portions to a strong acid such as sulfuricacid while keeping the temperature below about 5 C., contacting the reaction mixture with a cadmium compound to form the cadmium salt of the diazoanilinealdehyde condensation product, adding an excess (based on the amount of acid present) of a soluble salt, e.g., barium chloride, which will precipitate the undesirable acid anion, e.g., sulfate as barium sulfate.
  • a soluble salt e.g., barium chloride
  • the precipitate containing the cadmium salt of diazo-aldehyde resin and barium sulfate, can then be extracted to give a solution containing the cadmium salt of the resin which can then be dried. It is especially advantageous, however, to extract the precipitate with hydrofluoric acid to remove residual soluble barium ions as a precipitate of barium fluoride.
  • This step results in a resin free from contaminating cations and upon further addition of a cadmium halide, e.g., cadmium chloride, results in a resin of higher cadmium salt content.
  • Additional steps such as using a lower alkanol, e.g., isopropanol, in the extraction procedures tend t reduce the water content of the resin on drying and thereby further stabilize the resin.
  • the presensitized, grained aluminum printing late prepared according to our specifications, may be handled and treated in use as is customary in the art.
  • the unexposed areas are removed and the plate lacquered, after which the plate is used on a lithographic printing press.
  • the sensitive layer for the lithographic plate can be exposed to visible light, ultraviolet light, infrared light, X-rays or to heat patterns in order to form differential areas for printing. It is possible to use light-sensitive organic compounds such as aliphatic and aromatic esters, hydrazides and amides of naphthoquinone-diazide-sulfonates, cinnamalonic acids, their substitution products and functional derivatives, diazonium salts of amino-diphenyl amines and their condensation products with formaldehyde, orthoand paraquinone diazides of benzals, anthracenes and heterocyclic systems, for example, quinoline, indazoles, benzimidazoles, diphenyloxides, also diazoketones, unsaturated ketones, orthoand paraiminoquinone diazides, derivatives of alkylnitronaphthalenesulfonates, nitroaldehydes, acenaphthene, stilbene, azi
  • Silver halide emulsions may also be used.
  • the subbing may be overcoated with a photoconductive layer havin a high electrical resistance which can be charged and subsequently discharged by light or heat as in electrophotography, for example, low or high molecular weight organic photoconductors, also mixtures thereof with resins.
  • photoconductors are oxadiazoles, imidazolones, triazole, oxazole, thiazoles, hydrozones, triazines, polyvinyl carbazole and polyvinyl oxazoles.
  • Useful resins may contain groups which tend to make the resins soluble in alkali, such groups include acid anhydride, carbonic acid, sulfonic acid, sulfonamide and sulfonimide groups, for example, polyvinyl polymers or mixed vinyl polymers, phthalic acid ester resins, alkyl resins, rosins and polyacrylic acid resins.
  • the lithographic plates of the invention are further characterized by good adhesion and produce good removal of the unexposed areas so that they can produce a large number of copies.
  • FIG. 1 shows a grained aluminum sheet 3 having thereon a hydrophilic layer produced by treatment with a titanyl salt complex 2 and having thereon a light-sensitive stabilized diazo resin 1.
  • FIG. 2 shows the structure of FIG. 1 following exposure to light and removal of the unexposed areas of the stabilized diazo resin.
  • Example 1 Teitanyl silicofluoride A sheet of brush-grained aluminum having a thickness of 5 mils is immersed in a solution of titanium complex prepared by agitating vigorously a solution of 750 ml. of distilled water in 50 ml. of 31.9% fluosilicic acid, while 10 ml. of tetraisopropyl titanate is added rapidly in a fine stream. The aluminum is then passed between two mechanically driven inch diameter rubber rolls under sufficient pressure to remove the excess solution. A very thin film of solution is thus obtained which dries rapidly at room temperature. Similar coatings are obtained on other supports including polymeric materials, paper, metal, etc.
  • Example 2 Titanyl peroxy phosphate To 740 ml. of water is added 10 ml. (16.9 g.) of phosphoric acid (0.1588 mol) and 30 ml. (33 g.) of 28% hydrogen peroxide (0.262 mol). Then with good agitation 10 ml. (9.55 g.) of tetraisopropyl titanate (0.0336 mol) is added. The result is an orange-yellow solution which is ready for coating. This solution is coated as in Example 1 to give a thin coating on the surface of the support.
  • Example 3 Preparation of a titanyl fluoborate coating solution
  • 750 ml. water is added 14.7 g. (0.0672 mole) of 40% fluoboric acid with sufficient stirring to mix.
  • 10.0 ml. (0.0336 mole) of tetraisopropyl titanate is added with good agitation.
  • the ortho-ester hydrolyzes immediately forming a white precipitate which gradually redissolves forming a clear solution.
  • This solution is then coated on a grained aluminum sheet, dried, and sensitized with a dilute aqueous solution of diazo resin as in Example 5.
  • the titanyl fluoborate solution produces a suitable hydrophilic printing surface. Similar coatings are obtained on the supports of Example 1.
  • Example 4 Preparation of a pertitanic acid coating composition Tetraisopropyl titanate is added to a dilute aqueous solution of hydrogen peroxide in the same manner as the previous example.
  • the white hydrolysis product rapidly turns yellow and gradually dissolves to produce a clear yellow solution.
  • a particularly useful composition for application as in Example 1 contains 0.045 mol/l. of titanium and 0.307 mole/l. of hydrogen peroxide.
  • the hydrophilic character of the surface obtained is enhanced by drying at an elevated temperature. Similar coatings are obtained on the supports of Example 1.
  • Example 5 A diazo resin is prepared by mixing 34 g. p-diazo diphenyl amine sulfate-zinc chloride double salt with g. concentrated sulfuric acid which has been cooled to a temperature of 10 C. The mixture is agitated while the temperature is maintained at less than 3 C. while 3.25 g. para-formaldehyde, and 6.05 g. anhydrous cadmium chloride are added. The viscosity increases over a period of approximately one-half hour and the mixture becomes homogenous. The mixture is then poured over g.
  • This resin is a stabilized diazo resin.
  • Example 6 The treated, grained aluminum of Examples 1 and 2 is then sensitized by immersing in a dilute 2%, aqueous solution of diazo resin, passed between two rubber rolls to remove the excess and dried. When exposed at approximately 24 inches through a negative with a high intensity 220 volt carbon arc in a Nu Arc Printer, the exposed portions are hardened.
  • the unexposed portions of the diazo resin are removed by washing with water.
  • the image is then lacquered with a commercially available image lacquer.
  • the plate is then put on the lithographic printing press and produces 90,000 satisfactory copies.
  • Example 7 Preparation of a preferred diazo resin sensitizer An 800 ml. beaker is equipped with a mechanically driven propeller type stirrer and external cooling is provided. To the reaction vessel is added 540 g. (5.35 moles) of 96% sulfuric acid followed by portion-wise addition of 138 g. (0.377 mole) of Sensitizer DP (para diazo diphenyl amine sulfate-zinc chloride double salt) with stirring at to C. until solution is complete. The mixture is then cooled and maintained at 0 C. during the gradual addition of 100 ml. (0.592 mole) of fluoboric acid followed by the addition of 13.0 g.
  • Sensitizer DP para diazo diphenyl amine sulfate-zinc chloride double salt
  • Example 8 Preparation of a diazo resin sensitizer II
  • a diazo resin sensitizer II In a 1,500 ml. glass beaker was placed 1,040 of 96% sulfuric acid. The beaker was suspended and equipped with a variable speed stirrer. The stirring acid was cooled below 0 C. with a Dry Ice-acetone bath.
  • the acid solution was poured over a mixture of 2,200 g. of crushed ice and a solution of 1 lb. of cadmium chloride in 600 ml. of water with good agitation. A 3 liter portion of isopropyl alcohol was added and the resultant slurry filtered. The precipitate was slurried in 4 liters of water and 3 moles (624 g.) of barium chloride added. The resultant precipitate was filtered off and subsequently extracted twice with 3 liter portions of 0.75 M HF solution and a third time with 2 liters of distilled water. The filtrates were combined and a solution of 1 lb. of
  • Example 9 When the stabilized diazo resins of Examples 7 and 8 are coated on to untreated grained aluminum sheet, they are found to have better stability on aging than similar coatings made using diazo materials prepared by previously known methods. The stability is particularly better when the diazo resins are coated on a support carrying a layer of the mentioned titanium complexes.
  • the solutions used to remove the unhardened areas of the diazo resin are not critical. Water may be used, but aqueous gum solutions known in the art are also useful. It will be appreciated that other lacquers available commercially may also be used.
  • the diazo resins which may be used in our invention are prepared, stabilized and used in the dark or under yellow light. Therefore, when these resins are coated'on the treated plate, the coating operation is carried out under appropriate safelight conditions.
  • Example 10 The treated grained aluminum of Examples 1 and 2 is sensitized by coating with light-sensitive polymers using the whirler coating technique.
  • Kodak Photo Resist yields a clean appearing image. When inked, 50 press copies are obtained on the lithographic press.
  • Kodak Metal Etch Resist is developed by tray development followed by water wash-off and compressed air dried down to yield a robust, clean appearing image. The image is resistant to prolonged rubbing.
  • Light sensitive compositions of the type described in US. patent 2,948610 are swab developed with 0.5% sodium carbonate to yield adherent,
  • a light-sensitive silver halide emulsion comprising the first gelatin layer containing an oxidizing developer and a second layer containing light-sensitive silver halide is coated on the treated support.
  • a satisfactory lithographic plate is obtained after activation and inking of the surface.
  • a process for preparing a stable, light-sensitive diazo resin comprising:
  • step (c) separating a mixture containing (i) said cadmium 'Salt of said diazo resin and (ii) said barium sulfate, from the reaction mixture of step (b),

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
US648036A 1964-02-27 1967-06-22 Process for preparation and separation of light sensitive stabilized diazo resins Expired - Lifetime US3417055A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
DEE28725A DE1299661B (de) 1964-02-27 1965-02-19 Verfahren zur Verbesserung der hydrophilen Eigenschaften der Traeger von fuer Flachdruckverfahren geeigneten Druckplatten
BE660255A BE660255A (fr) 1964-02-27 1965-02-25
NL6502350A NL6502350A (fr) 1964-02-27 1965-02-25
GB38572/67A GB1108560A (en) 1964-02-27 1965-02-26 Preparation of a diazo resin salt
NO156951A NO115071B (fr) 1964-02-27 1965-02-26
GB8295/65A GB1108559A (en) 1964-02-27 1965-02-26 Lithographic printing plate
DK103065AA DK124245B (da) 1964-02-27 1965-02-26 Titanholdigt overtræksmateriale til litografiske trykkeplader.
SE2495/65A SE315909B (fr) 1964-02-27 1965-02-26
CH267065A CH435335A (fr) 1964-02-27 1965-02-26 Composition de revêtement
US505041A US3486450A (en) 1964-02-27 1965-10-24 Color proofing system
US648036A US3417055A (en) 1964-02-27 1967-06-22 Process for preparation and separation of light sensitive stabilized diazo resins
US658559A US3419406A (en) 1964-02-27 1967-08-04 Coating compositions
NO16987267A NO124113B (fr) 1964-02-27 1967-09-26
SE8622/68A SE320385B (fr) 1964-02-27 1968-06-26
US871607A US3694251A (en) 1964-02-27 1969-11-14 Coated article having a layer of boehmite and alkyl titanate

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US347931A US3342601A (en) 1964-02-27 1964-02-27 Lithographic printing plate
US648036A US3417055A (en) 1964-02-27 1967-06-22 Process for preparation and separation of light sensitive stabilized diazo resins
US658559A US3419406A (en) 1964-02-27 1967-08-04 Coating compositions

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US3417055A true US3417055A (en) 1968-12-17

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US648036A Expired - Lifetime US3417055A (en) 1964-02-27 1967-06-22 Process for preparation and separation of light sensitive stabilized diazo resins
US658559A Expired - Lifetime US3419406A (en) 1964-02-27 1967-08-04 Coating compositions

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US658559A Expired - Lifetime US3419406A (en) 1964-02-27 1967-08-04 Coating compositions

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US (2) US3417055A (fr)
BE (1) BE660255A (fr)
CH (1) CH435335A (fr)
DE (1) DE1299661B (fr)
DK (1) DK124245B (fr)
GB (2) GB1108559A (fr)
NL (1) NL6502350A (fr)
NO (1) NO115071B (fr)
SE (2) SE315909B (fr)

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DE69029104T2 (de) 1989-07-12 1997-03-20 Fuji Photo Film Co Ltd Polysiloxane und positiv arbeitende Resistmasse
GB9003079D0 (en) * 1990-02-12 1990-04-11 Alcan Int Ltd Lithographic plates
GB2350841B (en) * 1999-06-08 2001-12-19 Kansai Paint Co Ltd Inorganic film-forming coating composition, preparation method therof and inorganic film-forming method
JP4469927B2 (ja) 2000-05-23 2010-06-02 Ｄｉｃ株式会社 感光性組成物およびこれを用いた平版印刷版原版、画像形成方法
US6736890B2 (en) * 2000-07-25 2004-05-18 Kansai Paint Co., Ltd. Coating material for forming titanium oxide film, method for forming titanium oxide film and use of said coating material
JP2002341536A (ja) 2001-05-21 2002-11-27 Kodak Polychrome Graphics Japan Ltd ネガ型感光性組成物およびネガ型感光性平版印刷版
JP4154466B2 (ja) * 2001-10-30 2008-09-24 関西ペイント株式会社 酸化チタン膜形成用塗布剤、酸化チタン膜形成方法及び酸化チタン膜で被覆された金属基材
JP4250490B2 (ja) 2003-09-19 2009-04-08 富士フイルム株式会社 平版印刷版用アルミニウム合金素板および平版印刷版用支持体
JP4410714B2 (ja) 2004-08-13 2010-02-03 富士フイルム株式会社 平版印刷版用支持体の製造方法
EP1712368B1 (fr) 2005-04-13 2008-05-14 FUJIFILM Corporation Procédé de fabrication d'un substrat pour plaque lithographique
JP2009208140A (ja) 2008-03-06 2009-09-17 Fujifilm Corp 平版印刷版用アルミニウム合金板の製造方法、ならびに該製造方法により得られる平版印刷版用アルミニウム合金板および平版印刷版用支持体
US20090260531A1 (en) 2008-04-18 2009-10-22 Fujifilm Corporation Aluminum alloy plate for lithographic printing plate, lithographic printing plate support, presensitized plate, method of manufacturing aluminum alloy plate for lithographic printing plate and method of manufacturing lithographic printing plate support
JP5296434B2 (ja) 2008-07-16 2013-09-25 富士フイルム株式会社 平版印刷版用原版
EP2481603A4 (fr) 2009-09-24 2015-11-18 Fujifilm Corp Plaque originale d'impression lithographique

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US3163633A (en) * 1961-01-25 1964-12-29 Azoplate Corp Method for the manufacture of polyfunctional diazonium halides
US3235382A (en) * 1962-04-03 1966-02-15 Kalle Ag Presensitized foil for planographic and offset printing
US3246986A (en) * 1961-08-07 1966-04-19 Azoplate Corp Diazo materials for screen process printing

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Publication number Priority date Publication date Assignee Title
US2679498A (en) * 1954-05-25 Atent office
US2714066A (en) * 1950-12-06 1955-07-26 Minnesota Mining & Mfg Planographic printing plate
US3163633A (en) * 1961-01-25 1964-12-29 Azoplate Corp Method for the manufacture of polyfunctional diazonium halides
US3246986A (en) * 1961-08-07 1966-04-19 Azoplate Corp Diazo materials for screen process printing
US3235382A (en) * 1962-04-03 1966-02-15 Kalle Ag Presensitized foil for planographic and offset printing

Also Published As

Publication number Publication date
SE320385B (fr) 1970-02-09
NO115071B (fr) 1968-07-15
DK124245B (da) 1972-10-02
CH435335A (fr) 1967-05-15
BE660255A (fr) 1965-06-16
GB1108559A (en) 1968-04-03
NL6502350A (fr) 1965-08-30
DE1299661B (de) 1969-07-24
US3419406A (en) 1968-12-31
GB1108560A (en) 1968-04-03
SE315909B (fr) 1969-10-13

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