US3904412A - Method for the preparation of planographic printing plates from silver images - Google Patents

Method for the preparation of planographic printing plates from silver images Download PDF

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US3904412A
US3904412A US402883A US40288373A US3904412A US 3904412 A US3904412 A US 3904412A US 402883 A US402883 A US 402883A US 40288373 A US40288373 A US 40288373A US 3904412 A US3904412 A US 3904412A
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silver
fixer
compound
image
aqueous
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Frans Philomena Serrien
Bernard Hippoliet Tavernier
Robert Joseph Pollet
Francis Jeanne Sels
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/42—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/28—Sulfur atoms
    • 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
    • G03F7/066—Organic derivatives of bivalent sulfur, e.g. onium derivatives

Definitions

  • Daniel ABSTRACT A method for the preparation of a planographic printing plate wherein a sheet material comprising an outer hardenable hydrophilic colloid layer on the surface of which is concentrated a silver image which has been formed at that surface from complexed silver halide by silver complex diffusion transfer process, is treated with an aqueous lithographic fixer having a pH-value in the range from about 4.5 to about 7.2 and containing 1. an 1ron(IlI) ammonium salt of an aliphatic dicarboxylic acid which at least superficially oxidizes said silver image 2. a precipitating agent for silver ions, and
  • the present invention relates to a method for the preparation of planographic printing plates by converting silver images into hydrophobic ink-receptive images and to liquid compositions for improving the ink receptivity of the silver images.
  • the thus prepared silver image is rendered hydrophobic with an aqueous liquid.
  • lithographic fixer which liquid has a pH-value between 7 and 12 and contains (1 hexacyanoferrateflll) ions.
  • said silver image is at least superficially oxidized, and (2) an organic compound that is at least in part dissolved in said liquid and which reacts with said oxidized silver to ren der said image hydrophobic.
  • the lithographic fixer described in the above-mentioned Patent Specification has particularly favourable hydrophobizing properties some disadvantages are associated therewith.
  • the cyanoferrateflll) ion under the defined condition of a relatively high pH is not inert with respect to the mercaptocompounds, which are the preferred compounds for the purpose cited under the above item (2).
  • the mercaptocompounds which are the preferred compounds for the purpose cited under the above item (2).
  • some of the hexacyanoferrate( III) ions become reduced and the thus formed cyanoferratefll) ions form a blue precipitate with the excess cyanoferrate(lIl) ions.
  • a further disadvantage associated with the use of a lithographic fixer containing hexacyanoferrate(lll) ions resides in the fact that these ions have to be kept carefully out of contact of acids, for acids set free the highly toxic hydrogen cyanide.
  • aqueous lithographic fixer having a pH- value in the range of about 4.5 to about 7.2 and containing:
  • a preferred precipitating agent is therefor a substance yielding iodide ions e.g. potassium iodide, forming the very poorly soluble silver iodide.
  • a preferred lithographic fixer combination of the present invention contains in admixture with the above-cited compounds (1) to (3) an aliphatic amino compound comprising at least 4 unbranched carbon atoms, preference being given to n-octylamine.
  • the pH of the fixer is kept within the above-cited range and preferably at 6 to 6.2 by means of the dicarboxylic acid used for preparing the iron(IlI) ammonium salt thus preventing the precipitation of Fe(OH)
  • a suitable amount of aliphatic amino compound is in the range of 10 to ml per litre.
  • a preferred iron(IlI) salt for use according to the present invention is iron(III) ammonium malonate.
  • a preferred lithographic fixer contains from 20 to g of iron(IlI) ions present in the form of iron(lll)ammonium malonate.
  • iron(lIl) ammonium salts are derived from the aliphatic dicarboxylic acids: oxalic acid, maleic acid and fumaric acid.
  • Preferred thione compounds correspond to the following structural formulae:
  • the thione compound No. 4 which is the most preferred one can be prepared according to the following reaction scheme:
  • thione-thiol compounds for use ac cording to the present invention belong to the class of imidazoline-Z-thiones and imidazolidine2-thiones and are e.g.
  • Compound 10 is prepared as described in J.Gen.Chem.
  • Compound 12 is prepared as described in Can. l.Chem. 32, 59 (1954).
  • a relatively high amount of thione or thiol com- 5 pounds can be incorporated in the aqueous fixer when it contains water-miscible solvents e.g. n-propanol or ethylene glycol monoacetate.
  • a suitable amount of organic thiol or thione com pound is in the range of 0.5 to 15 g per litre.
  • a preferred lithographic fixer according to the present invention is composed as follows:
  • ) salt 20 g to 120 g ss 5 N potassium iodide 5 40 g organic solvenNs) npropanol 0 ml 200 ml ethylene glycol monoacetate 0 ml 150 ml water to make 1 1 pH adjusted to 6-6.2 by means of malonic acid and ammonium hydroxide.
  • the iron(lll) salt is present in the form of iron(lll) ammonium malonate.
  • Optimum results were obtained by using a fixer solution prepared by the following procedure: into 780 ml of an iron(lll)ammonium malonate solution containing 10.4% by weight of iron(lll)ions 39 ml of n-octylamine were dissolved whilst stirring. Subsequently after adding 1 ml of n-propanol and ml of ethylene glycol monoacetate, 39 ml of a 10% by weight solution of the thione compound N0. 4 in highly concentrated aqueous ammonium hydroxide were added. The pH was adjusted to 5.0 by means of additional aqueous ammonium hydroxide whereupon 23 g of potassium iodide were dissolved in the obtained composition.
  • the iron(lll)ammonium malonate solution was prepared by dissolving 570 ml of iron(lll)chloride in water in an amount sufficient to obtain a volume of 3 1.
  • 480 ml of ammonium hydroxide were added.
  • the obtained precipitate was stirred for 2 h at room temperature and separated by suction whereafter it was freed from chloride ions by washing with water.
  • the precipitate was redispersed in 3 l of water whereupon 750 ml of malonic acid dissolved in 1500 ml of water were added. Stirring was continued for l h.
  • the precipitate dissolved gradually in about 24 h.
  • the green solution obtained was filtered and further diluted with water up to a final volume of 7 l.
  • the con centration of iron(lll) ions was 104 g per litre.
  • the preparation of a planographic printing plate by using a fixer according to the present invention may be effected with a sheet material comprising a silver image obtained by any of the silver complex diffusion transfer processes hereinafter described by way of example.
  • a first type of silver complex diffusion transfer process utilizes a light-sensitive material and a separate image-receiving material constituting the said sheet material and containing on an outer surface thereof substance(s) for promoting the deposition of silver in the said silver complex diffusion transfer process.
  • the lightsensitive material comprises a water-permeable hydrophilic colloid layer on top of the said silver halide emulsion layer.
  • a water-permeable hydrophilic colloid layer on top of the said silver halide emulsion layer.
  • imagereceiving material can be used as described in United Kingdom Patent Specifications 1,013,344 and 1,054,252.
  • the incorporation of developing agents and preservatives thereof into the light-sensitive and/or image-receiving material for diffusion transfer processes is described in United Kingdom Patent Specifications 1,093,177 1,000,115 1,012,476 l.()42,477 1,054,253 and 1,057,273.
  • Embodiments in which hardening agents and more particularly latent hardening agents are incorporated into the light-sensitive and/or image'- receiving material for such processes are described in United Kingdom Patent specification 962,483 and German Patent Specification 1,203,604.
  • a second type of silver complex diffusion transfer process utilizes a single material.
  • a single material comprises a silver halide emulsion layer and may comprise a hardenable hydrophilic colloid layer, either beneath or above such silver halide layer.
  • Substances for bringing about the appearance of the diffusion transfer image (development nuclei) from the diffusing complexed silver halide may be present at an outer surface of the material or at an interface of the said layer(s). In the latter arrangement the silver image obtained by diffusion transfer is obtained on top of hardenable hydrophilic colloid layer and preferably is hydrophobized thereon.
  • the colloid layer with the silver image obtained by diffusion transfer is transferred to another sheet material, which may then be converted to a planographic printing plate for instance as described in the United Kingdom Patent Specification l ,001 ,55 8.
  • the development nuclei may be supplied in a liquid medium to the hardenable hydrophilic colloid layer on top of the light-sensitive silver halide emulsion layer.
  • the development nuclei depositing at the outer surface of the said layer make that the diffusion transfer silver deposition thus occurs at this outer surface.
  • the silver image areas are converted into ink-receptive printing areas to form a planographic printing plate with the lithographic fixer of the present invention.
  • the development nuclei may be applied to the surface of the light-sensitive recording material in the alkaline processing liquid for carrying out the diffusion transfer image formation or from a separate liquid composition containing such nuclei which constitutes a step after the exposure of the light-sensitive material and before wetting with the alkaline processing liquid for forming the diffusion transfer image.
  • Substances for promoting the silver deposition from the diffusing complexed silver halide 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 suitable too.
  • the complexed salts of lead and zinc sulphides are active both alone and when mixed with thioacetamide, dithiobiuret, and dithiooxamide.
  • Heavy metals, preferably silver, gold, platinum, palladium, and mercury may be used in their colloidal form.
  • the support of the photographic material comprising the silver halide emulsion layer may be any conventional flexible support sheet e.g. a paper sheet or a transparent hydrophobic film support, such as a support of cellulose triacetate or of a polyester e.g. polyethylene terephthalate.
  • the image sharpness of the silver pattern 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 layer and 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 in which the exposure is carried out, viz. at the front side or through the support. Preferably a red or black antihalation dye or pigment is used.
  • any silver halide emulsion of the negative or direct-positive type may be used depending on the nature of the original to be reproduced.
  • emulsions of the negative type are used, having a somewhat high sensitivity suitable for use in a camera.
  • the exposure of the silver halide emulsion layer may be carried out according to any usual technique e.g. by contact, by back reflection, by transmission or episcopically. Usually an episcopic exposure in a camera is carried out, particularly when the development nuclei are provided on top of the silver halide emulsion layer as detailedly described hereinafter.
  • the silver halide emulsion layer generally comprises an amount of silver halide equivalent to from 0.5 g.sq. metre to 1.5 g sq.
  • the sheet materials suited for use with the fixer solution of the invention are generally of simple composition. and may comprise a suitable support such as transparent hydrophobic film support or a paper sheet, either in direct contact or indirectly, e.g., by means of a suitable subbing layer, with a hydrophilic colloid outer layer having at its surface a pattern of finely divided silver particles.
  • a silver halide emulsion layer may be present between the colloid outer layer and the support and also antihalation dyes or pigments are provided.
  • the silver pattern obtained by the complex diffusion transfer process may be intensified by chemical or physio-chemical after-treatment for intensifying the silver pattern in or at the surface of the outer colloid layer.
  • a photographic material which comprises successively a support layer (preferably a paper support), an antihalation layer, a silver halide emulsion layer and develop ment nuclei on top thereof.
  • the said photographic material has to be kept for a period of time, e.g. for about l seconds, in the dark after it has been wetted with the alkaline processing liquid for carrying out the diffusion transfer image formation.
  • the application of the lithographic fixer composition may take place during the period the multi-layer material is kept in the dark. However. this application of lithographic fixer may also occur thereafter.
  • a photographic material comprising development nuclei on top of the silver halide emulsion layer may be provided in roll-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.
  • hydrophilic colloid outer layer any hardenable hydrophilic colloid is suitable.
  • gelatin is favoured, other hardenable hydrophilic colloids such as polyvinyl, alcohol, casein, carboxymethylcellulose and sodium alginate can be used too, the nature of the hardener used being dependent on the type of hydrophilic colloid to be hardened.
  • lf gelatin is used for forming the hydrophilic colloid outer layer, it may be submitted to a treatment as described in the United Kingdom Patent Specification 883,843 in order to improve the printing characteristics of the planographic printing plate.
  • Hardening of the hydrophilic colloid layer may occur before, during or after the treatment with the lithographic fixer composition and must occur at least to such an extent that no substantial amount of colloid is transferred on printing either to the rollers for applying water and ink to the printing plate or to the material to be printed.
  • hardening i.e. insolubilizing in water and strengthening against mechanical damage
  • the said hardening mostly occurs before the treatment with lithographic fixer.
  • the said hardening may be effected by addition of the generally known hardening agents for gelatin and similar col loids, such as formaldehyde, glyoxal, mucochloric acid and chrome alum, to the coating composition of the outer layer, at the surface of which the silver pattern will be produced, and/or to the coating composition of another layer, with which the said outer layer is in water-permeable relationship whereby hardening of the said outer layer takes place by diffusion of hardener from said other layer to said outer layer.
  • the generally known hardening agents for gelatin and similar col loids such as formaldehyde, glyoxal, mucochloric acid and chrome alum
  • 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 silver pattern.
  • the said hardening may be effected by incorporating a latent hardeners in one or more layers of the sheet material, whereby a hardener is released at the stage of the application of an alkaline processing liquid for carrying out the complex silver diffusion transfer process.
  • latent hardeners are active only in a well defined pH-range, mostly the pH-range of the usual developing liquids.
  • hardening of the outer hydrophilic colloid layer can also occur after the production of the silver pattern namely by treatment with a hard ening liquid.
  • This liquid may be an aqueous hardening composition applied before the treatment with the lithographic fixer, the fixer composition itself, or an aqueous hardening composition applied after the treatment with the said fixer.
  • At least one compound for improving the hydrophilic properties of the non-printing areas may be applied during the preparation of the printing plate.
  • hydrophilic colloid binders e.g. carboxymethylcellulose, gum arabic, sodium alginate, propyleneglycol ester of alginic acid, hy-
  • hygroscopic substances e.g. sorbitol, glycerol, tri(hydroxyethyl)ether of glycerol and turkey red oil, and certain wetting agents, may be present.
  • the hydrophilic colloid layer also may advantageously comprise a pigment particles homogeneously dispersed therein to 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).
  • 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 520 g sq.cm of the hydrophilic colloid outer layer are present.
  • a similar antiscumming effect may also be obtained by adding at least one member selected from colloidal silica, an inorganic acid eg o-phosphoric acid, a hygroscopic substance hereinbefore described and a suitable wetting agent to the fountain solution used during the printing process.
  • Suitable wetting agents include:
  • the lithographic fixer of the present invention is very stable to airial oxidation and to temperature fluctuations and it is suited for the production of planographic printing plates having non-staining image background parts.
  • the treatment with the aqueous lithographic fixer starts the outer colloid layer showing the silver pattern may be in a dry or wet condition.
  • a superficial oxidation of the silver pattern suffices, al-
  • the treatment with the lithographic fixer does not last long, mostly not longer than about 20 seconds and can be accelerated by increasing the concentration of the components in the said 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 lithographic fixing step is carried out just before printing.
  • the lithographic fixer as well as the development or activating liquid for the production of the diffusion transfer image can be applied in different ways, eg by spraying, by rubbing with a roller, or by dipping the material to be treated in the liquid composition.
  • the lithographic fixing step of the printing plate may proceed automatically by conducting the plate through a device having a narrow channel filled with the fixer composition and conveying the printing plate at the end of the channel between two squeezing rollers removing the excess of liquid.
  • the production of a silver image on top of the outer hydrophilic colloid layer and the treatment with the fixed may occur in a compact processing unit comprising both the processing stations.
  • the sheet material After the application of the lithographic fixer the sheet material is ready for inking and use as a printing plate. Treatment of the material with a lacquer composition for strengthening the printing parts is not necessary. Nevertheless, in some cases the hydropobic character of the ink-receptive parts and their mechanical strength may be improved by applying a lacquer thereon.
  • 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, monoethyl ether of diethylene glycol, tetrahydrothiophenel,1-dioxide, diacetone alcohol, dioxane, 1,2-dichloroethane, ethyl acetate, trichloroethylene, butyl butyl-ate. diethanolamine and dimethylformamide. Mixtures of such organic solutions with an aqueous phase or dispersions of such organic solutions in an aqueous phase are also suitable.
  • the aqueous phase may contain thickeners or other 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 Patent Specifications 967,598 968,706 1,004,342 1,071,163 and 1,071,164.
  • Resins that have proved to be especially suitable for improving the ink-receptive character of the printing areas and strengthening them are phenol-formaldehyde resins e.g. phenolformaldehyde resins, a-eresol formaldehyde resins, and p-tert.-butylphenol formaldehyde resins, alkyd resins e.g. rosin maleic acid esters, epoxy resins. condensation productsof a poly( aryl ethylene oxide) with an acid anhydride, an amine or another suitable compound and epoxidized polyesters.
  • the resin, wax or oil is usually used in a concentration of from about to about 500 g per litre 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. When an emulsion lacquer is used the plate needs not necessarily 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 e.g. with a plugof wadding.
  • the hydrophobic solid substances settle on the image areas and improve the hydrophobic ink-receptive character thereof. At the same time the mechanical strength of the printing areas is improved.
  • the adherence of the lacquer to the printing areas may further be improved by heating the plate.
  • the liquid lacquer composition may also be incorporated with the aqueous composition containing the iron(lIl) ammonium salt of an aliphatic dicarboxylic acid and the organic compounds for converting the silver image in a hydrophobicink-receptive pattern.
  • the ratio of the organic phase that contains the hydrophobic solid substances to the aqueous phase is generally between 1:] and 1:10.
  • the printing plate has to be wet at the stage the greasy printing ink is applied. This is generally known in the art and it is usual to apply an aqueous liquid before applying the printing ink. This may occur by means of a wet sponge or by means of the fountain arrangements (damping system) of the printing machine.
  • the iron(lll) salt is present in the form of iron( 111) ammonium malonate.
  • the material thus obtained was a positive planographic printing plate with very good printing characteristics and with which more than 1000 copies of high quality could be printed. Applying a lithographic lacquer in order to strengthen the printing parts was not necessary and could be omitted.
  • the fountain solution used on printing could be water or liquid having the following composition:
  • the light-sensitive material obtained was image-wise exposed and then dipped for 10 sec. in the following processing liquid:
  • the material was then rubbed for some 15 seconds with a plug of wadding saturated with the lithographic fixer described in Example 1, wherein, however, thione compound 4 had been replaced by a same amount of mercapto compound I.
  • 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 weight 135 g per sq.m; a highsensitive silver chlorobromide gelatin emulsion layer comprising hydroquinone and l-phenyl-3- pyrazolidinone was applied so that per sq.m are present, an amount of silver halide equivalent to l g of silver nitrate, l g of hydroquinone and 0.5 g of l-phenyl- Il-pyrazolidinone.
  • the material obtained after this treatment was readly for use as planographic printing plate with positive image values compared to the original. More than 1000 copies could be printed therewith.
  • the fountain solution might be mere water or the specific fountain com position of Example 1.
  • EXAMPLE 4 To a strong paper support of weight 135 g per sq.m a thin gray antihalation was applied by pouring a dispersion of 3 g of lamp black in 1 litre ofa 4% aqueous solution of gelatin at a rate of 1 litre per 40 sq.m.
  • a high-sensitive silver chlorobromide gelatin emulsion layer comprising hydroquinone and 1-phenyl-3-pyrazolidinone was applied in such a way that per sq.m. were present: an amount of silver halide equivalent to l 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:
  • This exposure might be an episcopic exposure in a camera or an exposure through an intermediate original having a sufficiently transparent background and being pressed with its rcarside against the nuclei side of the multilayer material.
  • the multilayer material can be used in roller form and after the image-wise exposure be cut off as desired.
  • the plate was then moistened (e.g. by means of a plug of wadding) for some 20 seconds with the following lithographic fixer composition:
  • the iron(lll) salt is present in the form of iron(lll) ammonium malonate.
  • the said fixer composition was very stable to aerial oxidation and to temperature fluctuations. With 1 litre thereof about 100 printing plates (21 cm X 29.7 cm size) could be prepared.
  • the preparation of the printing plate proceeded 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 based on the original. It was mounted on an offset apparatus and after having been wetted with water or other fountain solution (e.g. a liquid composed of ml of water, 10 ml of glycerol, 2 ml of colloidal silica and 2 ml of phosphoric acid), the fatty printing ink was applied and printing started. More than 1000 copies were printed with the plate thus prepared.
  • water or other fountain solution e.g. a liquid composed of ml of water, 10 ml of glycerol, 2 ml of colloidal silica and 2 ml of phosphoric acid
  • a method for preparing a planographic printing plate wherein a sheet material comprising an outer hardenable hydrophilic colloid layer on the surface of which is concentrated a silver image which has been formed at that surface from complexed silver halide by silver complex diffusion transfer process is contacted with an aqueous lithographic fixer having a pH-value in the range from about 4.5 to about 6.2 and containing:
  • said lithographic fixer contains as said iron( III) salt from 20 to 120 g of iron(lll) ammonium malonate per litre.

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US402883A 1972-10-04 1973-10-03 Method for the preparation of planographic printing plates from silver images Expired - Lifetime US3904412A (en)

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GB4579272A GB1435900A (en) 1972-10-04 1972-10-04 Method for the preparation of planographic printing plates

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4160670A (en) * 1976-08-10 1979-07-10 Mitsubishi Paper Mills, Ltd. Lithographic printing plate material
US4165237A (en) * 1975-05-16 1979-08-21 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
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
US4355090A (en) * 1979-07-04 1982-10-19 Mitsubishi Paper Mills, Ltd. Method for making a diffusion transfer lithographic printing plates with oxazolidones
US4357407A (en) * 1980-10-09 1982-11-02 Agfa-Gevaert N.V. Production of reverse reading positive images of a straight reading original
US4361635A (en) * 1981-06-19 1982-11-30 Minnesota Mining And Manufacturing Company Photolithographic element containing a silver-receptive polyaldehyde-containing receiving layer
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
US4603100A (en) * 1985-03-14 1986-07-29 Minnesota Mining And Manufacturing Company Silver image enhancement composition and process for use thereof
US5153097A (en) * 1988-03-03 1992-10-06 Mitsubishi Paper Mills Limited Light-sensitive material for lithographic printing plate and process for making printing plate
US5272044A (en) * 1989-11-02 1993-12-21 Fuji Photo Film Co., Ltd. Silver halide photographic material and processing solution and process for the processing thereof
EP0678786A1 (en) * 1994-04-19 1995-10-25 Agfa-Gevaert N.V. A method for making a lithographic printing plate
US5525455A (en) * 1993-08-19 1996-06-11 Mitsubishi Paper Mills Limited Treating solution for lithographic printing plate
US20070026342A1 (en) * 2005-07-29 2007-02-01 Fromson Howard A Imageable printing plate for on-press development

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IL51654A0 (en) * 1976-04-26 1977-05-31 American Cyanamid Co New non-asymmetric synthesis of tetramisole levamisole and their derivatives
US5064745A (en) * 1988-02-25 1991-11-12 Mitsubishi Paper Mills, Ltd. Method for making lithographic printing plate
JPH0756349A (ja) * 1993-08-19 1995-03-03 Mitsubishi Paper Mills Ltd 平版印刷版用版面処理液

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US3490906A (en) * 1964-10-06 1970-01-20 Du Pont Process for preparing printing plates and developer compositions therefor
US3721559A (en) * 1967-06-19 1973-03-20 Agfa Gevaert Nv Photographic material for the preparation of printing plates
US3615507A (en) * 1968-12-13 1971-10-26 Eastman Kodak Co Photographic bleach-fix solutions
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Cited By (17)

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Publication number Priority date Publication date Assignee Title
US4062682A (en) * 1974-11-12 1977-12-13 Agfa-Gevaert N.V. Fixer compositions used in planographic printing containing onium compounds
US4165237A (en) * 1975-05-16 1979-08-21 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
US4160670A (en) * 1976-08-10 1979-07-10 Mitsubishi Paper Mills, Ltd. Lithographic printing plate material
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
US4355090A (en) * 1979-07-04 1982-10-19 Mitsubishi Paper Mills, Ltd. Method for making a diffusion transfer lithographic printing plates with oxazolidones
US4357407A (en) * 1980-10-09 1982-11-02 Agfa-Gevaert N.V. Production of reverse reading positive images of a straight reading original
US4361635A (en) * 1981-06-19 1982-11-30 Minnesota Mining And Manufacturing Company Photolithographic element containing a silver-receptive polyaldehyde-containing receiving layer
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
US4603100A (en) * 1985-03-14 1986-07-29 Minnesota Mining And Manufacturing Company Silver image enhancement composition and process for use thereof
US5153097A (en) * 1988-03-03 1992-10-06 Mitsubishi Paper Mills Limited Light-sensitive material for lithographic printing plate and process for making printing plate
US5272044A (en) * 1989-11-02 1993-12-21 Fuji Photo Film Co., Ltd. Silver halide photographic material and processing solution and process for the processing thereof
US5525455A (en) * 1993-08-19 1996-06-11 Mitsubishi Paper Mills Limited Treating solution for lithographic printing plate
EP0678786A1 (en) * 1994-04-19 1995-10-25 Agfa-Gevaert N.V. A method for making a lithographic printing plate
US20070026342A1 (en) * 2005-07-29 2007-02-01 Fromson Howard A Imageable printing plate for on-press development
US7816065B2 (en) 2005-07-29 2010-10-19 Anocoil Corporation Imageable printing plate for on-press development

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BE805519A (nl) 1974-04-01
DE2349527A1 (de) 1974-04-18

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