Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
  • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
  • C07D285/135—Nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
  • C07D249/12—Oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
  • C07D249/14—Nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • 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
• • 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

• the present invention relates to planographic printing and more especially to planographic forms which are produced by transforming photographic silver images into hydrophobic ink-receptive images.
• silver images produced photographically can be converted by means of a bleaching or toning process or by reducers or intensifiers with the aid of oxidation baths into sparingly soluble heavy metal and/ or silver salt images.
• potassium ferricyanide is used for example for oxidizing the silver, whereby the silver image is converted into ferrocyanide, which is precipitated partly as insoluble silver ferrocyanide and partly as insoluble ferrocyanide of other metals, which are added to the baths in the form of salts.
• ferricyanides and ferric salts are used. It is also known to intensify with potassium ferricyanide and lead salts.
• planographic printing forms can be made by way of a silver image, the converted silver image being capable of taking up greasy printing ink, if silver images are converted by oxidation into images of heavy metal and/ or silver compounds and these are reacted with organic compounds which contain SH, SeI-I, OH or NH groups and therefore can form organic salt-like or complex compounds with the heavy metal and/ or silver ions of the compounds formed by the oxidation, the organic heavy metal and/or silver compounds being more sparingly soluble than these lastmentioned compounds.
• Suitable organic compounds are those which are sparingly soluble in water, that is to say the solubility of which in water at a temperature of 20 C is lower than 0.1 percent by weight.
• the insolubility of these compounds is effected by suitable substituents such as aryl, aralkyl, cycloalkyl, and alkyl radicals, preferably one or more long-chained straight or branched chain, saturated or unsaturated hydrocarbon radicals with at least 10, preferably to carbon atoms.
• substituents such as aryl, aralkyl, cycloalkyl, and alkyl radicals, preferably one or more long-chained straight or branched chain, saturated or unsaturated hydrocarbon radicals with at least 10, preferably to carbon atoms.
• such compounds are especially suitable which contain SH or SeH groups, which can be in a tautomeric form, if the carbon atom carrying these groups is further bonded to two further hetero atoms, heterocyclic compounds having an OH group bonded to a heterocyclic carbon atom and heterocyclic compounds having a cyclically bonded NH group, because these constitutions ensure at the same time a good solubility of the compounds in alkaline solutions and a low solubility of the heavy metal and/or silver salts obtained with these compounds.
• furyl, thia'zolyl which substituents are either linked to one of the two atoms Y and Z, directly or by means of other linking groups, or linked to one of the ring elements of the heterocyclic ring.
• R represents aryl (phenyl, tolyl), aralkyl (benzyl), and alkyl, preferably a long-chained straight or branched chain, saturated or unsaturated hydrocarbon radical with at least 8 carbon atoms, which is linked to one of the ring atoms, directly or by way of one or more intermediate members.
• N it stands for a live or six-membered heterocyclic ring such as a triazole, imidazole, and pyrimidine ring; and R represents an aryl (phenyl, tolyl), aralkyl (benzyl), an alkyl (4) Mercaptans (C H SH, C H SH) (5) Thioarnides (-C H CSNH C H CS.NH
• an imagewise exposed silver halide layer is immersed in a silver halide developing solution containing a silver halide solvent such as sodium thiosulfate and then brought into contact with a light insensitive hydrophilic transfer layer, such as a gelatine layer.
• a silver halide solvent such as sodium thiosulfate
• unexposed silver halide of the silver halide layer is dissolved and transferred into the transfer layer Where it is reduced by the silver halide developing solution to a silver image.
• the silver halide solvent may also be incorporated into the transfer layer, whereasthe developing substance, such as hydroquinone, may be incorporated into the silver halide layer.
• the transfer layer may also contain small catalytic amounts of developing nuclei, such as silver sulphide.
• Paper is an example of a suitable support for the planegraphic printing form, if this paper is coated with a waterresisting but nevertheless hydrophilic layer, for example with a hardened gelatine layer or superficially saponified cellulose acetate.
• a waterresisting but nevertheless hydrophilic layer for example with a hardened gelatine layer or superficially saponified cellulose acetate.
• matting agents such as TiO SiO BaSO which are inert with respect to ferrocyanides and ferricyanides. These matting agents may be applied in quantities of about 5-100 percent as calculated on the Weight of binding agent.
• the support for the planographic printing form it is furthermore possible to use plates consisting of metals alloys, or their oxides, if such oxidizing baths are used which are chemically inert with respect to said plates. Using such plates, it is possible even without any preliminary treatment to produce a silver image thereon, when they are brought into contact with an exposed negative layer in a suitable developer which contains a solvent for silver halide.
• Other supports which are suitable are plastic supports having a sufficiently hydrophilic surface, for example superficially saponified acetyl cellulose foil. It is advantageous to ensure that such plates and foils are provided with development nuclei for example silver sul phide before they are processed, so that the reduction of the silver salts takes place at sufiicient speed during the silver salt diifusion process.
• Suitable for oxidizing the silver images are all combinations of an oxidizing agent with an anion by means of which there are formed heavy metal salts and/or silver salts which are still soluble and available for subsequent conversion into the organo-metallic compounds. These are preferably baths by means of which silver chloride, silver bromide, silver ferrocyanide or combined silver and heavy metal ferrocyanides and ferricyanides are formed i.e. combinations of copper sulphate with (31- ions or K Fe(CN) As oxidizing baths there are also suitable aqueous solutions of oxidizing agents which transform the silver of the images at least superficially into silver oxide, such as solutions of Water soluble permanganates, dichromates and iodic acid.
• the silver image may be oxidized with a solution of a ferricyanide which is soluble in aqueous solution, the oxidation being effected in the presence of metal salts the metal ions of which form. ferrocyanides and/ or ferricyanides which are insoluble in aqueous solution, so that insoluble ferrocyanides, or co-precipitates of insoluble ferrocyanide and ferricyanide oxidizing salts are precipitated at the place of the silver image.
• it is advantageous to add to the treating bath complex formers Which are capable of dissolving Waterinsoluble metal ferricyanides.
• composition of the conversion baths for the silver image depends mainly on the cation which, in addition to the silver of the silver image, should form an insoluble ferrocyanide with the reduced ferricyanide.
• the metal cations concerned can be subdivided into two groups, depending on their behaviour:
• group A Included in group A are the cations which form an insoluble deposit only with a ferrocyanide, such as for example lanthanum lead thorium and uranyl (U For this group, it is necessary to have a conversion bath containing the following constituents:
• a salt of a metal of this group the said salt being soluble in water or in weak acids, such as lanthanum, ace tate, lead nitrate, thorium nitrate, uranylnitrate;
• a water-soluble fern'cyanide for example alkali metal or alkaline earth metal ferricyanides such as K Fe(CN) Na Fe(CN),,-, Li Fe(CN) if desired, it is also possible for an acid to be added.
• group B Included in group B are the cations which would also form an insoluble deposit with the 'ferricyanide of the bath, such as for example silver, copper, zinc, cadmium,
• the conversion bath must contain the following constitu-V ents: i t
• a salt of a metal of this gnoup the said salt being soluble in water or in weak acids, such as silver nitrate, copper sulfate, zinc sulfate, zinc chloride, cadmium sulfate, manganese sulfate, manganese chloride, iron chloride, cobalt nitrate, cobalt sulfate, nickel nitrate, and zinc acetate;
• a complex former or chelating agent which prevents the metal ferricyanide from precipitating or forming a colloidal solution, such as for example iron without however preventing the formation of insoluble ferrocyanides during the silver conversion.
• a water-soluble ferricyanide for example alkali, metal or alkaline earth metal fenicyanides such as An acid can, if desired, also be added in order to adjust the pH value to about 3-6.
• soluble citrates, ttartrates or oxalates or ammonia are suitable as complex formers.
• Suitable acids are inorganic and organic acids, however, such acids are preferred which have the same anion as the complex former.
• metal salts mentioned above those of iron, cobalt, nickel, copper, zinc and the uranyl group yield particularly good results, but the salts of silver, lanthanum, thorium, lead and manganese are also suitable for the process.
• These metal salts can be used individually or in admixture with one another.
• the part of the bath containing the soluble ferricyanide is preferably kept separate from the solution with the remaining constituents, since prepared baths containing all the constituents are in many cases not stable for a very long time, this being in contrast to the separate component solutions.
• the proportion of metal salt is approximately 1 to 10 g. per 200 cc. of the total bath; the proportion of the soluble fern'cyanide is about 0.5 to 2 0 g. per 200 cc. of the total bath.
• the proportion of the complex former required with cations of group B is different in each case and must be chosen to be so small that, on the basis of the decomposition constants of the metal complex, the reaction comprizing the conversion of silver and the separation of insoluble ferrocyanide (possibly with the entrainment of ferricyanide) takes place quickly.
• the end of the conversion can in every case be recognized by the complete disappearance of the color of the superficial and usually black image, and this can be observed particularly easily when the precipitated ferrocyanide and the ferricyanide which may be entrained therewith have a light color.
• the ferrocyanide is light green and the ferricyanide is yellow.
• the organic compounds are applied in the form of at least partially aqueous solution, either by immersion or rubbing.
• an alkaline agent is added to produce better solubility of the organic compounds, whereby simultaneously an increase in the reaction velocity is produced.
• suitable silver salt solvents for example ammonia or potassium-thiocyanate, the deeper portion of the image can also be included in the reaction.
• the organic compounds are preferably used in concentrations of 2-100 g. per litre of solution.
• solvent there is preferably used water in combination with alkali agents such as hydroxides of alkaline metals (sodium, potassium, lithium), ammonia, and/ or quaternary ammonium bases such as tetramethylamrnonium hydroxide.
• alkali agents such as hydroxides of alkaline metals (sodium, potassium, lithium), ammonia, and/ or quaternary ammonium bases such as tetramethylamrnonium hydroxide.
• watermiscible organic solvents preferably propanol in quantities up to about 60 percent calculated on the volume of the total solution.
• the pH value of the solution may vary within wide limits, pH values of about 8 to 14 being pre ferred.
• the solubility product of the inorganic compound preferably amounting to about 10* to and that of the organic compounds to about 10" to 10*.
• Example 1 A lacquered water-resisting paper base is coated with a layer containing gelatine as binder, catalytic amounts of colloidal silver and a solvent for silver halide, preferably sodiumthiosulfate (1 g. per 10 g. of gelatine). The layer is hardened with formalin.
• a positive of a line original or type-written original is produced on the foil by the silver salt diffusion process, for example as described in German Patent No. 887,733, according to which a silver halide emulsion layer is exposed to the object to be reproduced, immersed in an ordinary silver halide developing solution containing hydroquinone as a developing substance and thereafter brought into contact with said foil.
• an ordinary silver halide developing solution containing hydroquinone as a developing substance and thereafter brought into contact with said foil.
• silver halide is dissolved out of the unexposed areas of the silver halide layer and transferred to the foil, where it is reduced by the developing solutions to a silver image which is positive as compared with the object to be reproduced.
• a suitable developing solution has for instance the following composition: water 1000 cc., p-methylaminophenolsulfate 2.5 g., hydroquinone 15., KBr 2 g., Na SO 100 g, NaOH 30 g.
• the silver image is bleached to silver chloride by immersing it into or rubbing it with a solution of 70 g. of K Fe(CN) 1000 ml. of water.
• the foil is rinsed for removing the bleaching solution and rubbed with a solution of 3.5 g. of 1amino-2mercapto-5-heptadecyl-1,3,41triazole ml. of 2 N sodium hydroxide solution,
• Example 1 A positive silver image bleached and rinsed as in Example 1 is rubbed with a solution of 4 g. of Z-mercapto-S-heptadecyl-1,3,4-triazole (II) in 10 ml. of 2 N sodium hydroxide solution, 7
• Example 3 A silver image bleached and rinsed as in Example 1 is rubbed with a solution of 4 g. of Z-mercapto 5 stearylmercapto 1,3,4 thiodiazole (III) in 10 ml. of 2 N sodium hydroxide solution,
• Example 4 A silver image bleached and rinsed as in Example 1 is rubbed with a solution of 5 g. of heptadecyl tetrazole (XIII), in 10 ml. of N sodium hydroxide solution, 20 ml. of propanol and 5 ml. of water,
• Example 6 Instead of being bleached with the K Fe(CN) bleaching bath, a silver image prepared as in Example 1 is rubbed with a solution of 100 g. CuSO 100 g. NaCl 7 r 25 ml. H (concentrated 1000 ml. H 0
• Example 7 Instead of being bleached with a K Fe(CN) bleaching bath, a foil prepared as in Example 1 is rubbed with a mixture of the two following solutions (A) 4 g. of ZnSOUH O,
• Example 8 The foil bleached and rinsed as 'in Example 1 is rubbed witha solution of 3 g. of dithiocarbazinic acid stearyl ester (VII) in 5 ml. of N sodium hydroxide solution,
• the further processing is as in Example 1. Up to 500 copies are obtained.
• Example 9 The foil bleached and rinsed as in Example 1 is rubbed with a solution of 3 g. of Z-heptadecyl-1,3,4-triazole (XII) in 5 ml. of N sodium hydroxide solution, ml. of propanol and 10 ml. of Water.
• XII Z-heptadecyl-1,3,4-triazole
• the further processing is as in Example 9. Up to 500 copies are obtained.
• Example 10 A silver image bleached and rinsed obtained as in Example 1 is bathed for 30 seconds in the following solution:
• the silver image may be treated for 30 seconds in the following solution:
• Example 11 A silver image obtained as in Example 1 is treated for 30 seconds in aqueous 5% potassium bichromate solution. After rinsing the silver image is bathed for 20 seconds in a solution of 20 g. of potassium methyl xanthogenate, 20 cc. of 2 N NaOH, and
• Example 12 A foil of cellulose acetate is coated with a thin layer of gelatine and ther after treated with a solution of colloidal silver to provide the surface of said layer with colloidal silver. On the thin treated foil there is produced a silver image as disclosed in Example 1.
• a silver image is oxidized by treating the foil for 20 seconds in an aqueous 2% potassium permanganate solution and thereafter in a solution of 10 which is diluted before use with 10 times its volume of water.
• the cited silver image there may also be used one which is produced in a hardened silver halide emulsion layer (2 parts of silver halide per 1 part of gelatine) coated on a foil of cellulose acetate or polyester of ethylene-glycol and terephthalic acid. A half-tone negative image is printed into said layer, which is developed and fixed in the ordinary processing bath. The image obtained is rinsed and thereafter treated as above.
• (V) Dithiocarbazinic acid stearyl ester 25 g. of the ammonium salt of dithiocarbamic acid are dissolved in 100 ml. of 2 N sodium hydroxide solution. After the addition of 67 g. of octadecyl bromide in 400 ml. of alcohol, the mixture is heated for 1 hour under reflux and thereafter filtered with suction when cold. The precipitate is melted under glacial acetic acid and freed from unreac-ted initial material by shaking. A compact waxlike mass with a melting point of 60-80 C. is obtained.
• a process for the production of planographic printing forms for printing with fatty inks comprising bleaching with a silver oxidizing bath an image of silver particles dispersed in a supported hydrophilic layer, to obtain a corresponding inorganic silver image having a solubility product within the range of about 10* to 10*, said silver oxidizing bath containing an inorganic oxidizing salt, then reacting said inorganic silver image with an alkaline solution of an organic compound selected from the group consisting of A H-N' R il+ no-o (v) ns-n and v1)
• RCS-NHa N represents a S-mcmbered heterocyclic ring and the group H g stands for a member selected from the class consisting of S-membered heterocyclic rings, 6-membered heterocylic rings and 5- and 6-membered heterocyclic rings fused together, obtaining a corresponding organic silver compound more sparingly soluble than said inorganic silver compound, and thereafter applying a fatty printing ink to said
• said oxidizing bath contains as said inorganic oxidizing salt a substantial amount of non-silver heavy metal ion, for converting said image into a corresponding inorganic silver compound and a compound of said heavy metal.
• said oxidiz ing bath contains as oxidizing agent a compound selected from the group consisting of water soluble ferricyanides,permanganates, and cuprihalogenides.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Printing Plates And Materials Therefor (AREA)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

Country Status (7)

Cited By (17)

Families Citing this family (12)

Citations (8)

• 0
  • NL NL227262D patent/NL227262A/xx unknown
  • BE BE567153D patent/BE567153A/xx unknown
• 1957
  • 1957-04-26 DE DEA27030A patent/DE1058844B/de active Pending
  • 1957-08-16 DE DEA27721A patent/DE1064343B/de active Pending
• 1958
  • 1958-04-23 CH CH5866758A patent/CH371960A/de unknown
  • 1958-04-23 US US730259A patent/US3083097A/en not_active Expired - Lifetime
  • 1958-04-26 FR FR1202369D patent/FR1202369A/fr not_active Expired
  • 1958-04-28 GB GB13442/58A patent/GB847436A/en not_active Expired

Patent Citations (8)

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