US3721559A - Photographic material for the preparation of printing plates - Google Patents

Photographic material for the preparation of printing plates Download PDF

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Publication number
US3721559A
US3721559A US00174140A US3721559DA US3721559A US 3721559 A US3721559 A US 3721559A US 00174140 A US00174140 A US 00174140A US 3721559D A US3721559D A US 3721559DA US 3721559 A US3721559 A US 3721559A
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colloid
stratum
layer
silver
emulsion layer
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Haes L De
H Gevers
J Vanheertum
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G03F7/063—Additives or means to improve the lithographic properties; Processing solutions characterised by such additives; Treatment after development or transfer, e.g. finishing, washing; Correction or deletion fluids

Definitions

  • a planographic printing plate is prepared from a photographic sheet material comprising a support, a light-sensitive silver halide emulsion layer and an exterior hydrophilic colloid stratum having at its free surface a pattern of finely divided silver particles, by contacting the same with an aqueous alkaline fixer composition containing an oxidizing agent for metallic silver and an organic thione, or mercapto tautomer thereof, for converting the pattern of silver particles into a hydrophobic ink-receptive pattern, the colloid stratum being hardened beforethe material is used for printing and preferably before or at least concurrently with its contact with said fixer composition, the extent of the hardening being at least that necessary to prevent removal of the colloid material during print ing.
  • the pattern of silver particles is produced by means of the silver complex diffusion transfer process in which insoluble development nuclei are applied to the free layer surface either from the diffusion transfer developing liquid or a separate liquid applied prior to the developing liquid.
  • the colloid stratum is hardened by means of a latent hardener released during the course of the diffusion transfer process.
  • 'colloid stratum can be an external stratum of the emulsion layer or a separate colloid layer applied to the emulsion layer.
  • development nuclei at the surface of the material, the development nuclei being present either on top of the said emulsion layer or on top of a hardenable hydrophilic colloid layer applied to said emulsion layer.
  • the diffusion transfer silver image produced in the photographic material according to the present invention is substantially situated at the surface of the material.
  • a planographic printing plate can be prepared very simply from the diffusion transfer copy obtained by one single treatment as will be described detailedly hereinafter.
  • the support sheet of the photographic material according to the invention maybe any usual flexible support sheet, e.g., a paper sheet or a transparent hydrophobic usual film support such as a support of cellulose triacetate or of a polyester, e.g., polyethylene terephthalate.
  • Any silver halide emulsion of the negative or direct positive type preferably a gelatin silver halide emulsion, may be used dependent on the nature of the original to be reproduced.
  • emulsions of the negative type having a rather high sensibitiy of the order as normally required for camera exposure are used.
  • the exposure of the silver halide emulsion layer can be carried out according to any usual technique, e.g., in contact, reflectographically, by transmission or episco'pically, mostly an episcopic exposure in a camera is carried out.
  • the silver halide emulsion layer preferably has a sensitivity of the order as normally required for camera exposure.
  • the silver halide emulsion layer generally comprises an amount of silver halide equivalent to from about 0.5 g to about 1.5 g of silver nitrate and preferably amounting only to the equivalent of about 1 g of silver nitrate. This means a considerable economy of silver halide with respect to the silver halide content of emulsion layers commonly used in the production of diffusion transfer copies. If necessary a suitable subbing layer is provided for strongly adhering the silverhalide emulsion layer to the support sheet.
  • the development nuclei may be provided directly on top of the silver halide emulsion layer. In that case it should be a hardenable one and preferably a gelatin silver halide emulsion layer. Preferably, however, one and sometimes even more other water-permeable layer(s) is (are) applied on top of the silver halide emulsion layer, the outer layer always being a hardenable hydrophilic colloid layer preferably a gelatin layer, on which the development nuclei have to be present.
  • the development nuclei are applied on top of the photographic material at the preparation stage by means of a specific after-treatment of the material with a liquid composition containing such nuclei.
  • a hydrophilic protective colloid e.g., gelatin
  • This amount of colloid does not suffice to form a layer and in most cases .is hardened at the hardening stage'of the hydrophilic colloid layer or by diffusion of hardener from said layer.
  • the development nuclei may also be supplied by a specific processing liquid with which the photographic material is wetted after the image-wise exposure and before the alkaline processing liquid for carrying out the diffusion transfer image formation is applied, or they may be incorporated into the said alkaline processing liquid itself.
  • Suitable development nuclei for being applied to the photographic material according to the present invention are sulphides of heavy metals such as the sulphides, of antimony, bismuth, cadmium, cobalt, lead, nickel, silver and zinc.
  • Other suitable salts are the selenides, polysulphides, polyselenides, mercaptans and tin(ll)halides.
  • Heavy metals or their salts and fogged silver halides are suitabletoo.
  • the complexed salts of lead and zinc sulphides are active alone as wellas mixed with thioacetamide, dithiobiuret, and dithiooxamide.
  • Heavy metals, preferably silver, gold, platina, palladium, and mercury may be used in their colloidal form. From these metals the noble metals are the most active ones.
  • Thedevelopment nuclei may be applied on top of the photographic material at the preparation stage or they may be incorporated into a processing liquid in the usual concentrations as generally known in the art.
  • hydrophilic colloid outer layer any hardenable hydrophilic colloid is suitable.
  • gelatin is favored, as already mentioned above, other hardenable hydrophilic colloids such as polyvinyl alcohol, casein, carboxymethylcellulose and sodium alginate can be used too. If gelatin is used for forming the hydrophilic colloid outer layer, it may be submitted to a treatment as described in the United Kingdom Pat. specification No. 883,843 filed Sept. 2,
  • the outer hydrophilic colloid layer i.e., the silver halide emulsion layer or an outer layer on top thereof, has to be hardened at the printing stage.
  • Hardening of the hydrophilic colloid binder of the outer layer may occur before, during or after the treatment of the diffusion transfer copy produced with the fixer composition for preparing the planographic printing plate and must occur at least to such an extent that no substantial amount of colloid is transferred on printing neither to the rollers for applying water and ink to the printing plate nor to the material to be printed.
  • hardening i.e., insolubilizing in water and strengthening against mechanical damage must occur at least to such an extent that the material obtained can be used as a planographic printing plate.
  • the said hardening mostly occurs before the said treatment with fixer.
  • the said hardening may occur by addition of the generally known hardening agents for gelatin and similar colloids such as fordevelopment nuclei in dispersion is applied on top of the said outer layer the hardeners can also be incorporated-into said coating composition.
  • Hardening of the hydrophilic colloid binder of the outer layer may also occur during the production of the diffusion transfer silver pattern by incorporating hardeners into at least one of the processing liquids and/or by incorporating latent hardeners into the photographic materi-- al to be hardened. These latent hardeners are active only in a well defined pH-range, mostly the pH-range of the usual alkaline processing liquid for carrying out the diffusion transfer image formation.
  • hardening of the outer hydrophilic colloid layer may also occur after the production of the silver pattern, viz. by treatment with a hardening liquid.
  • This liquid may be an aqueous hardening composition applied before the treatment with the fixer, the fixer composition itself or an aqueous hardening composition applied after the treatment with the fixer.
  • the exposure latitude of the photographic material according to the present invention in most cases can be prolonged considerably. Also the image sharpness of the silver pattern can be increased and, as a consequence thereof, the sharpness of the final result of printing can be improved by applying antihalation dyes or pigments. These dyes or. pigments may be present in the .silver halide emulsion layer or in the support, but preferably are incorporated into a layer situated between the silver halide emulsion layerand the support. If a transparent support is used the antihalation dyes or pigments may be applied to the rear side of the material or on top of the emulsion layer dependent on the manner inwhich the exposure is carried out, viz. atv
  • the front side or through the support Preferably a red or black antihalation dye or pigment is used. If the antihalation layer is gray the correctness of the exposure can easily be controlled 1 by judging the diffusion transfer image in transmittance before carrying out the fixing step.
  • the photographlcmaterial according to the present invention may comprise at least partof the compounds that are essential or useful for carrying out the diffusion transfer image formation such as developing. agents, preservatives for these developing agents, complexing agents, stabilizers, alkaline substances, black-toning agents, hardeners and softening agents in the materials used, whereby the aqueous processing liquid can be reduced to an aqueous solution of alkaline substances described in the United Kingdom Pat. specification No. 1,013,343 filed Dec. 29, 1961 by Gevaert Photo Producten N.V..
  • developing agent(s) mostly hydroquinone and a 3-pyrazolidinone developing compound used together
  • hygroscopic substances likewise called hydrophilic softening agents, e.g. sorbitol, glycerol,trihydroxyethyl ether of glycerol and turkish red oil, and certain wetting agents,
  • hydrophilic colloid layer will improve the hydrophilic properties of the non-printing areas.
  • the hydrophilic colloid outer layer also may advantageously comprise a considerable amount of pigment particles that will prevent the so-called scumming (i.e., ink-acceptance that arises in the non-printing areas of the printing plate after a certain number of copies has been printed).
  • the usual inorganic pigments e.g., barium sulphate, titanium dioxide, china clay and silica applied from a colloidal solution, have proved to be particularly suitable for this purpose.
  • the pigment particles are generally homogeneously applied in such an amount that about 5-20 g thereof are present per sq.m. of the hydrophilic colloid outer layer.
  • a similar anti-scumming effect may also be obtained by addingat least one mern'ber selected of colloidal silica, an inorganic acid, e.g., o-phosphoric acid, a hydrophilic softening agentas those mentioned above and a suitable wetting agent to the fountain solution used during the printing process.
  • Suitable wetting agents are,
  • a very suitable fountain solution comprises water, glycerol, o-phosphoric acid and colloidal silica.
  • the material is first image-wise exposed to an original. This may occur according to any usual technique as detailedly described above.
  • the material is then treated with an aqueous alkaline processing liquid for carrying out the diffusion transfer image formation in the presence of a developing agent, a complexing agent for silver halide and development nuclei on top of the outer hardenable hydrophilic colloid layer.
  • the said aqueous alkaline processing liquid may be applied in different ways, e.g., by spraying, by rubbing, with a lick roller, or by dipping the photographic material in the liquid composition.
  • the photographic material In order to obtain a diffusion transfer silver deposition that will be sufficiently dense, the photographic material has to be kept for a short while, e.g., for about 10 seconds, in the dark afterit has been wetted with the alkaline processing liquid for carrying out the diffusion transfer image formation.
  • the application of the fixer composition may already take place during the period the multilayermaterial is kept in the dark. However, this application of fixer may also occur thereafter.
  • the photographic material comprising development nuclei on top of the silver halide emulsion layer may be provided in roller form.
  • image-wise exposure e.g., an episcopic exposure in a camera or an exposure through a transparent original in contact with the photographic material
  • the latter may be guided automatically through a usual processing unit containing the alkaline processing liquid and comprising guiding and driving means as generally known in the art.
  • a usual processing unit containing the alkaline processing liquid and comprising guiding and driving means as generally known in the art.
  • an empty tray with loose roller which is lifted by the material during cutting, may be provided between the exposure unit and the processing unit.
  • planographic printing plate from the photographic material carrying at its surface a diffusion transfer silver pattern may occur according to any technique for producing a planographic printing plate from a sheet material having'a hardenable hydrophilic colloid outer layer carrying at its surface a pattern of silver particles.
  • the photographic material carrying the diffusion transfer silver image at its surface is treated with a fixer being an aqueous treating composition buffered at a pH value from 7 to 12 and to which have been added potassium cyanoferrateflll) and an organic compound that converts the pattern of silver particles in a hydrophobic ink-receptive pattern.
  • a fixer being an aqueous treating composition buffered at a pH value from 7 to 12 and to which have been added potassium cyanoferrateflll) and an organic compound that converts the pattern of silver particles in a hydrophobic ink-receptive pattern.
  • Potassium cyanoferrateglll mostly is incorporated into the fixer in a concentration of from 25 to 300 g'per liter and may simply be added by dissolving it in the aqueous fixer composition.
  • the effect of the present invention may also be obtained by using other generally known oxidizing agents for silver particles instead of potassium cyanoferrateflll) even by using such agents that only in a very minor amount produce silver ions at the surface of the silver pattern such as water-soluble cadmium, strontium or calcium salts.
  • the good results obtained by using potassium cyanoferrate(III) as an oxidizing agent cannot be obtained by using other oxidizing agents. This is very unexpected since there exist many oxidizing agents having a better oxidizing power than potassium cyanoferrate(IlI).
  • organic compounds that have proved to be especially suitable for this purpose are thioxo compounds, including the tautomeric structures thereof, making the silver image ink-receptive, e.g.
  • imidazoline-Z-thiones and imidazolidine-Z-thiones including the N-substit'uted derivatives such as imidazolidine-4-on-2-thiones including substituted derivatives such as phenyltetrazoline-thiones including derivatives such as tetrahydro pyrimidine-Z-thiones including substituted derivatives such as tetrahydroand -dihydro-oxazine-2 -thiones and thiazine-Z-thiones including substituted derivatives such as l,3,4-dihydro thiadiazine-Z-thiones including sub- ,7
  • thiourea compounds including substituted derivatives preferably N-phenyl thiourea compounds such (ll) CH: S
  • the compounds that convert the silver image parts in hydrophobic ink-receptive parts may be added directly to the fixer, but are often added from an aqueous alkaline solution or from a solution in a suitable organic, water-miscible solvent such as ethanol, isopropanol,
  • ethylene glycolmonomethyl ether and dimethylformamide They must be at leastpartially soluble in the fixer composition. They are mostly applied in an' amount of from 0.5to 5 g per liter of fixer. it is remarkable that most of the suitable compounds for converting the silver image parts in ink-receptive parts are black-toning agents generally known in the silver complex diffusion transfer process.
  • the fixer composition is buffered at a pH value from 7 to 12. Very often it is buffered at a pH of about 8-9. Hereby its stability is considerably improved. Any compound or-combination of compounds having a buffering action in the indicated pl-l region is suitable.
  • Sodium' hydrogen carbonate and sodium tetraborate have proved to be especially suited for this purpose as well as the following combinations of compounds sodium carbonate and sodium hydrogen carbonate, sodium carbonate and citric acid, sodium carbonate, sodium hydrogen carbonate and citric acid, boric acid and sodium tetraborate, and trisodium phosphate and oleic acid.
  • the compound or compounds for buffering the fixer may be applied in the usual concentrations generally known to those skilled in the art.
  • the fixer may comprise some further compounds'for improving the hydrophilic ink-repellent properties of the non-printing areas. Suitable such compounds are colloidal silica and hydrophilic colloid binders, hydro philic softening agents, inorganic acids and wetting agents already mentioned and exemplified above.
  • the fixer may also contain compounds for improving the ink-receptive character of the printing areas such as higher fatty acids, e.g. oleic acid, and hydrophobic softening agents, e.g., dimethyl phthalate, dibutyl phthalate, the phthalic acid ester with the following formula
  • the fixer composition used in carrying out the method of the present invention is very stable to aerial oxidation and to temperature fluctuations and it may be used for the production of many printing plates without having to frequently adjust the processing time. Many printing plates (about 100 plates of 21 cm X 29.7 cm size per liter of fixer) can be produced before the fixer composition is fully exhausted.
  • the outer colloid layer showing the silver pattern may be in dry as well as in wet condition.
  • a superficial oxidationof the silver pattern suffices; generally, however, a more penetrating oxidation is advantageous.
  • the treatment with the fixer does not last long, mostly no longer than about seconds and can be accelerated by increasing the concentration of the components present in the fixer.
  • the plate may be stored for a long time before being fixed and even thereafter it may be stored for a long time before being used in the printing process.
  • the fixing step is carried out just before printing.
  • the fixer can be applied in different ways, e.g., by spraying, by rubbing, with a lick roller, or by dipping the material to be treated in the liquid composition.
  • the fixing step of the printing plate may occur automatically by conducting the plate through a device having a narrow channel filled with the fixer composition and at the end thereof between two squeezing rollers.
  • a device having a narrow channel filled with the fixer composition and at the end thereof between two squeezing rollers In order to reduce the risk for aerial oxidation of the fixer to a minimum, funnel-shaped inand outlet openings may be provided at the ends of the narrow channel and an upperlying plastic bag containing the fixer liquid may be used. If the apparatus is not used, the bag is moved downwards and the fixer runs back from the channel into the bag.
  • aqueous phase are suitable too.
  • the aqueous phase may contain thickeners or other usual compounds for improving the hydrophilic character of the non-printing areas of the lithographic printing plate as described above.
  • Suitable lacquers are described in the United Kingdom Pat. specifications No. 967,598 filed Feb. 6, 1961 by Kalle, 968,706 filed June 2, 1961 by Geva ert Photo-Producten N.V., 1,0,04,342 filed July 17, 1962 by Kalle, 1,071,163 and 1,071,164 both filed Apr. 30, 1964 by Gevaert Photo-Producten N.V.
  • Resins that have proved to be especially suitable for improving the ink-receptive character of the printing areas and strengthening them are phenol-formaldehyde acid esters, epoxy resins e.g. condensation products of a poly aryl ethylene oxide) with an acid anhydride, an amine or another suitable compound and epoxidized polyesters.
  • the resin, wax or oil used mostly is present in a concentration of from about 100 to about 500 g per liter of liquid lacquer composition.
  • the liquid lacquer composition may be applied after the aqueous composition containing. the oxidizing agent has been applied and while the printing plate is still wet. Only when an emulsion lacquer is used the plate need not necessarily to be wet at the stage the lacquer is applied.
  • the lacquer may be applied by dipping, spraying, spreading or by means of a material soaked therewith. The lacquer is rubbed out, e.g., with a plug of wadding.
  • the hydrophobic solid 1 substances settle on the image areas and improve the
  • the production of the diffusion transfer silver image on top of the photographic material (occasionally including the image-wise exposure of the silver halide emulsion layer) and the treatment with the fixer may occur automatically, e.g., in processing stations as described above, and occasionally can be carried out both in a compact processing unitcomprising both processing stations.
  • the sheet material After the application of the fixer the sheet material is ready for use as a printing plate. This means that no further treatment with a lacquer composition for strengthening the printing parts is necessary.
  • Suitable lacquer compositions are solutions of oils, waxes and resins in organic solvents.
  • Suitable organic solvents are cyclohexanone, acetone, butanol, monomethyl ether of ethylene glycol, monethyl ether of diethylene glycol, tetrahydrothiophene-l,l-dioxide, diacetone, dioxane, 1,2-dichloroethane, ethyl acetate, trichloroethylene, butyl butyrate, diethanolamine and dimethylformamide.
  • the liquid lacquer composition may also be mixed with in the aqueous composition containing potassium cyanoferrateflll') and the organic compound for converting the silver image in a hydrophobic ink-receptive pattern.
  • the ratio of the organic phase that contains the hydrophobic solid substances to the aqueous phase then mostly is comprised between H1 and H10.
  • the printing plate has to be wet at the stage the fatt printing ink is applied. This is generally known in the art and it is usualto apply an aqueous liquid before applying the printing ink. This mayoccur by means of a wet sponge or by means of the fountain arrangement of the printing machine This wetting has to be more intensive as the printing plate is more dry, e.g. when it has been stored for a long time after its fixation and occasional lacquering.
  • the silver halide gelatin emulsion layer After drying of the silver halide gelatin emulsion layer, said layer was overcoated at a rate of 20 g per sq.m with the following development nuclei composition water 890 ccs 12.5 aqueous saponin ccs aqueous colloidal nickel sulphide dispersion comprising per 100 ccs 0.2 g of nickel sulphide and 10 g of gelatin 7 100 ccs.
  • the photographic material thus obtained was exposed to an original and treated for 30 sec. in the following processing composition sodium hydroxide to g anhydrous sodium sulphite 75 g potassium bromide l g hydroquinone 16 g l-phenyl-3-pyrazolidinone 1 g water up to 1,000 ccs anhydrous sodium thiosulphate 10 g.
  • fixer composition The material was then rubbed for somev 20 seconds with a plug of wadding saturated with the following fixer composition:
  • the light-sensitive material obtained was exposed image-wise and for 10 sec. dipped. in the following processing liquid water 1,000 ccs sodium phosphate-ll-water 75 g anhydrous sodium sulphite 40 g potassium bromide 0.5 g anhydrous sodium thiosulphate 10 g aqueous colloidal nickel sulphide dispersion of example 1 In this way, a positive diffusion transfer silver image was produced at the surface of the silver halide emul-. sion layer.
  • the material was then rubbed for some 15 seconds with a plug of wadding saturated with the fixer described in example 1, wherein, however, compound (3) had been replaced by a same amount of compound (2).
  • the printing plate thus prepared could be used for printing in the same manner as described in example 1 and about the same good results were obtained.
  • EXAMPLE 3 To a paper support of 135 g per sq.m a common high-sensitive silver chlorobromide. gelatin emulsion layer comprising hydroquinone and l-phenyl-3- pyrazolidinone was applied in such away that per sq. m were present, an amount of silver halide equivalent to 1 g of silver nitrate, 1 g of hydroquinone and 0.5 g of 1- phenyl-S-pyrazolidinone.
  • the silver halide gelatin emulsion layer After drying of the silver halide gelatin emulsion layer, said layer was overcoated at arate of g per sq.m with the followingcomposition water 926 ccs gelatin 10 g 12.5 aqueous saponin 8 ccs 20 aqueous formaldehyde 56 ccs Thenthe following liquid was applied in a proportion of 22 g per sq.m
  • the photographic light-sensitive material obtained was exposed image-wise and then guided through an automatic two-bath processing device, thehaths, of which had the following compositions respectively l activating liquid) water a 1,000 ccs sodium phosphate-12-water 75 'g anhydrous sodium sulphite 40 g potassium bromide 0.5 g anhydrous sodium thiosulphate 10 g H.
  • the material obtained after this treatment was ready for use as planographic printing plate with positive image values in respect of the original. More than 1,000 copies could be printed therewith.
  • the fountain solution might be mere water or thefspecific fountain composition of example 1.
  • EXAMPLE 4 To an extra strong paper support of g per sq.m a thin gray antihalation layer was applied by pouring a dispersion of 3 g of lamp black in 1 liter of a 4'percent aqueous solution of gelatin at a rate of 1 liter per 40 sq.m.
  • a common high-sensitive silver chlorobromide gelatin emulsion layer comprising hydroquinone and l-phenyl-3-pyrazolidinone was applied in such'a way that per sq.m there were present an 20 ccs y al was guided through a processing amount of silver halide equivalent to 1 g of silver nitrate, l g of hydroquinone and 0.5 g of l-phenyl-3- pyrazolidinone.
  • the silver halide gelatin emulsion layer was overcoated at a rate of 100 g per sq.m with the following composition water 926 ccs gelatin 10 g 12.5 aqueous saponin 8 ccs 20 aqueous formaldehyde 56 ccs Then the following liquid was applied at a rate of 22 g per sq.m
  • aqueous saponin 10 cos aqueous colloidal nickel sulphide 'nuclei dispersion comprising per 100 ccs 0.2 g of nickel sulphide and 10 g of gelatin 100 ccs.
  • the plate was then moistened (e.g., by means of a plug of wadding) for some 20 seconds with the following fixer composition:
  • the preparation of the printing plate might occur automatically in a compact processing unit comprising the successive treating stations and wherein the plate was transported automatically from one unit to the other.
  • the printing plate thus obtained was ready for use as a planographic printing plate with positive image values in respect of the original. It was braced on a usual offset apparatus and after having been we'tted with water or another usual fountain solution (e .g., a liquid composed of 90 ccs of water, 10 ccs of glycerol, 2 ccs of colloidal silica and 2 cos of phosphoric acid), the fatty printing ink was applied and printing started. More than 1,000 copies were printed with the plate thus prepared.
  • water or another usual fountain solution e .g., a liquid composed of 90 ccs of water, 10 ccs of glycerol, 2 ccs of colloidal silica and 2 cos of phosphoric acid
  • fixer composition aqueous sodium carbonate 30 cos 5 aqueous sodium hydrogen carbonate 30 ccs potassium cyanoferrateflll
  • fixer compositions 10 aqueous sodium carbonate 30 cos 5 aqueous sodium hydrogen carbonate 30 ccs potassium cyanoferrateflll
  • aqueous sodium carbonate 30 cos 5 aqueous sodium hydrogen carbonate 30
  • ccs potassium cyanoferrateflll 10.75 g 10
  • I solution of l-allyl-imidazolidine- 2-thione in ethylene glycol monomethyl ether 4 ccs distilled water up to 100 ccs
  • the pH-value of this buffered fixer composition amounted to 10.2.
  • a printing plate was prepared as described in example 4, with the difference, however, that the gelatin layer directly on the silver halide emulsion layer was applied from the following coating composition water 926 ccs gelatin 5.6 g 12 1: aqueous saponin 8 ccs 20 k aqueous formaldehyde 56 ccs propylene glycol ester of alginic acid 20 g A printing plate was still improved printing characteristics was obtained.
  • a method of preparing a planographic printing plate from a photographic sheet material comprising a light-sensitive silver halide emulsion layer and an exterior hardenable hydrophilic colloid stratum which comprises:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2500448A1 (de) * 1974-01-07 1975-07-10 Minnesota Mining & Mfg Photolithographische platte und verfahren
US3904412A (en) * 1972-10-04 1975-09-09 Agfa Gevaert Nv Method for the preparation of planographic printing plates from silver images
US4062682A (en) * 1974-11-12 1977-12-13 Agfa-Gevaert N.V. Fixer compositions used in planographic printing containing onium compounds
US4144064A (en) * 1977-09-26 1979-03-13 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
US4149889A (en) * 1976-03-15 1979-04-17 Mitsubishi Paper Mills, Ltd. Direct offset printing plate
US4220702A (en) * 1977-12-15 1980-09-02 Mitsubishi Paper Mills, Ltd. Method for making a lithographic printing plate
US4223087A (en) * 1976-06-09 1980-09-16 Minnesota Mining And Manufacturing Company Method of making plate oleophilic
US4224402A (en) * 1978-10-03 1980-09-23 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
US4230792A (en) * 1976-07-15 1980-10-28 Mitsubishi Paper Mills, Ltd. Lithographic printing plate from silver halide emulsion
DE3016732A1 (de) * 1979-05-02 1980-11-06 Mitsubishi Paper Mills Ltd Fotografisches material zur herstellung von druckplatten und verfahren zu dessen herstellung
US4297429A (en) * 1979-06-18 1981-10-27 Mitsubishi Paper Mills, Ltd. Photographic material and diffusion transfer processing solution for making printing plates and method for making printing plates
US4454216A (en) * 1981-06-23 1984-06-12 Mitsubishi Paper Mills, Ltd. Method for making improved lithographic printing plate
US4563410A (en) * 1982-02-19 1986-01-07 Agfa-Gevaert N.V. Method for the preparation of a planographic printing plate using NiS containing nuclei
US4606985A (en) * 1981-09-02 1986-08-19 Mitsubishi Paper Mills, Ltd. Lithographic printing plates
US4824760A (en) * 1986-04-11 1989-04-25 Mitsubishi Paper Mills, Ltd. Lithographic printing plate with benzotriazoles improved in printing endurance
US5236802A (en) * 1991-03-06 1993-08-17 Mitsubishi Paper Mills Limited Lithographic printing plate with polyacrylamide polymer in physical development nuclei layer
US5391457A (en) * 1991-11-05 1995-02-21 Fuji Photo Film Co., Ltd Preparation of lithographic printing plate with thioether solvents
EP0742491A1 (en) * 1995-05-12 1996-11-13 Fuji Photo Film Co., Ltd. Platemaking process with heat developable silver salt diffusion transfer
US6284426B1 (en) * 1993-02-09 2001-09-04 Agfa-Gevaert Process solution and method for making a lithographic aluminum offset plate by the silver salt diffusion transfer process
BE1014695A3 (fr) 2001-03-12 2004-03-02 Mitsubishi Paper Mills Ltd Methode de fabrication d'une plaque d'impression lithographique.
EP1700710A1 (en) 2005-03-08 2006-09-13 Konica Minolta Medical & Graphic, Inc. Printing method, sheet material and mounting method of printing plate

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EP0644461B1 (en) * 1993-09-21 1997-04-23 Agfa-Gevaert N.V. A method for making a lithographic printing plate
EP0691578A3 (en) 1994-03-22 1996-07-17 Agfa Gevaert Nv Image recording element and method for producing a printing form by the method of silver salt diffusion transfer
EP0745901B1 (en) 1995-05-31 1999-03-17 Agfa-Gevaert N.V. A concentrated dampening solution with an improved shelf life for printing with a lithographic printing plate obtained according to the silver salt diffusion transfer process
EP0750227B1 (en) 1995-06-23 1999-09-22 Agfa-Gevaert N.V. Imaging element and method for making lithographic printing plates according to the silver salt diffusion transfer process
EP0779554A1 (en) 1995-12-14 1997-06-18 Agfa-Gevaert N.V. A correcting liquid for a silver imaged lithographic printing plate
EP0791858B1 (en) 1996-02-26 2000-10-11 Agfa-Gevaert N.V. A method for making by phototypesetting a lithographic printing plate according to the silver salt diffusion transfer process

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Publication number Priority date Publication date Assignee Title
BE538152A (instruction) * 1952-05-03
BE556753A (instruction) * 1956-04-18

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904412A (en) * 1972-10-04 1975-09-09 Agfa Gevaert Nv Method for the preparation of planographic printing plates from silver images
DE2500448A1 (de) * 1974-01-07 1975-07-10 Minnesota Mining & Mfg Photolithographische platte und verfahren
US4062682A (en) * 1974-11-12 1977-12-13 Agfa-Gevaert N.V. Fixer compositions used in planographic printing containing onium compounds
US4149889A (en) * 1976-03-15 1979-04-17 Mitsubishi Paper Mills, Ltd. Direct offset printing plate
US4223087A (en) * 1976-06-09 1980-09-16 Minnesota Mining And Manufacturing Company Method of making plate oleophilic
US4230792A (en) * 1976-07-15 1980-10-28 Mitsubishi Paper Mills, Ltd. Lithographic printing plate from silver halide emulsion
US4144064A (en) * 1977-09-26 1979-03-13 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
US4220702A (en) * 1977-12-15 1980-09-02 Mitsubishi Paper Mills, Ltd. Method for making a lithographic printing plate
US4224402A (en) * 1978-10-03 1980-09-23 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
DE3016732A1 (de) * 1979-05-02 1980-11-06 Mitsubishi Paper Mills Ltd Fotografisches material zur herstellung von druckplatten und verfahren zu dessen herstellung
US4297429A (en) * 1979-06-18 1981-10-27 Mitsubishi Paper Mills, Ltd. Photographic material and diffusion transfer processing solution for making printing plates and method for making printing plates
US4454216A (en) * 1981-06-23 1984-06-12 Mitsubishi Paper Mills, Ltd. Method for making improved lithographic printing plate
US4606985A (en) * 1981-09-02 1986-08-19 Mitsubishi Paper Mills, Ltd. Lithographic printing plates
US4563410A (en) * 1982-02-19 1986-01-07 Agfa-Gevaert N.V. Method for the preparation of a planographic printing plate using NiS containing nuclei
US4824760A (en) * 1986-04-11 1989-04-25 Mitsubishi Paper Mills, Ltd. Lithographic printing plate with benzotriazoles improved in printing endurance
US5236802A (en) * 1991-03-06 1993-08-17 Mitsubishi Paper Mills Limited Lithographic printing plate with polyacrylamide polymer in physical development nuclei layer
US5391457A (en) * 1991-11-05 1995-02-21 Fuji Photo Film Co., Ltd Preparation of lithographic printing plate with thioether solvents
US6284426B1 (en) * 1993-02-09 2001-09-04 Agfa-Gevaert Process solution and method for making a lithographic aluminum offset plate by the silver salt diffusion transfer process
EP0742491A1 (en) * 1995-05-12 1996-11-13 Fuji Photo Film Co., Ltd. Platemaking process with heat developable silver salt diffusion transfer
US5700622A (en) * 1995-05-12 1997-12-23 Fuji Photo Film Co., Ltd. Platemaking process with heat developable silver salt diffusion transfer
BE1014695A3 (fr) 2001-03-12 2004-03-02 Mitsubishi Paper Mills Ltd Methode de fabrication d'une plaque d'impression lithographique.
EP1700710A1 (en) 2005-03-08 2006-09-13 Konica Minolta Medical & Graphic, Inc. Printing method, sheet material and mounting method of printing plate

Also Published As

Publication number Publication date
DE1771627A1 (de) 1971-04-08
CH518577A (de) 1972-01-31
DE1772677A1 (de) 1971-05-27
NL161591B (nl) 1979-09-17
NL161591C (nl) 1980-02-15
DE1772677B2 (de) 1981-06-11
AT294135B (de) 1971-11-10
FR1583235A (instruction) 1969-10-24
CH517324A (de) 1971-12-31
SE359938B (instruction) 1973-09-10
FR1582133A (instruction) 1969-09-26
NL6808599A (instruction) 1968-12-20
BE716778A (instruction) 1968-12-19
GB1241661A (en) 1971-08-04
DE1772677C3 (de) 1982-02-18

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