US3063837A - Photographic diffusion transfer process for planographic printing - Google Patents

Photographic diffusion transfer process for planographic printing Download PDF

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Publication number
US3063837A
US3063837A US850769A US85076959A US3063837A US 3063837 A US3063837 A US 3063837A US 850769 A US850769 A US 850769A US 85076959 A US85076959 A US 85076959A US 3063837 A US3063837 A US 3063837A
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United States
Prior art keywords
silver
emulsion
silver halide
layer
image
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Expired - Lifetime
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US850769A
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English (en)
Inventor
Lassig Wolfgang
Gunther Eberhard
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Agfa Gevaert NV
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Agfa AG
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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
    • G03F7/066—Organic derivatives of bivalent sulfur, e.g. onium derivatives

Definitions

  • the present invention relates to planographic printing and more especially to planographic printing forms which are produced by transforming soluble silver complex salts which are imagewise distributed in a colloid layer, into hydrophobic greasy ink-receptive silver salt images.
  • a modification of the process consists in that the sodium thiosulphate is not added to the transfer layer, but to the silver halide developer solution.
  • the production of the images is based on the fact that unexposed and consequently undevelopable silver halide of the negative is dissolved by the silver halide solvent whereafter the soluble silver complex formed difiuses into the transfer layer.
  • the silver complex is reduced on the development nuclei by means of the silver halide developer solution to produce a metallic silver image which with respect to the original is positive and not laterally inverted.
  • the image silver is first of all converted by oxidation into a sparingly soluble inorganic silver compound or into inorganic compounds of silver and/or of other heavy metals such as for example ferrocyanides, ferricyanides, silver chloride, silver bromide, silver oxide and others. Thereafter, by means of a second processing liquid, the silver ions and/or other heavy metal formed by the oxidation are reacted with organic compounds to form organic hydrophobic silver compounds which are more sparingly soluble than said in organic compounds, whereafter greasy printing ink is applied to said hydrophobic images.
  • the silver serving for the production of the greasy ink-receptive image consequently experiences the following reactions:
  • a silver halide emulsion layer is exposed to the object to be reproduced, developed in a silver halide developer solution to produce a silver image and treated with a silver halide solvent to transform at least part of the unexposed silver halide into a soluble silver complex compound, which soluble silver complex compound is transferred to a colloid layer to produce a colloid layer containing therein in imagewise distribution said silver complex compound, whereafter said colloid layer is treated with an alkaline aqueous solution of an organic mercapto compound preferably containing an aliphatic hydrocarbon radical having 8 to 20 carbon atoms to transform said soluble silver complex compound into a positive image of the object to be reproduced consisting essentially of a hydrophobic silver compound of said mercapto compound, said hydrophobic silver compound image being then dyed with a greasy printing ink.
  • the negative materials and developers usually used in the production of silver images by the silver salt diffusion process are suitable for carrying out the present process.
  • the silver halide emulsions of the negative layer are silver chloride emulsions, silver chlorobromide emulsions (1-99 percent AgCl+99-l percent of AgBr) and silver bromide emulsions, which may also contain small amounts of silver iodide (about 1-5 percent) although silver halide emulsion devoid of silver iodide are preferred.
  • silver chloride emulsion and with silver chlorobromide emulsion the silver halide of which contains not more than percent by weight of silver bromide.
  • These emulsion layers may contain organic silver halide developers such as hydroquinone, p-methylaminophenol as it is well known in the art.
  • the aqueous developer solutions usually contain an alkaline metal hydroxide, an organic silver halide developer substance such as hydroquinone, l-phenyl-3-pyrazolidone p-methylaminophenol, a preserving agent such as a watersoluble sulphite and silver halide solvents, such as for example sodium thiosulphate, potassium thiocyanate, ammonia or organic amine bases, the alkali metal thiosulphates being preferred.
  • the pH value is about 9-13.
  • the positive layer serving as printing form is a hardened hydrophilic colloid layer applied to a paper or film support, the hydrophiiic colloid being preferably hardened gelatine (ll0 g./rn. If it is desired to keep the developer solution free from silver halide solvents or to decrease the amount of said solvents in the developer so lutions the colloid layer will have added thereto a sufiicient quantity of one of the aforesaid silver halide solvents preferably alkali metal thiosulphates (1-50 percent by weight as calculated on the amount of binding agent). In order to produce a good water conduction of the printing forms, addition of inert fillers, such as for example barium sulphate, strontium sulphate, may also be provided.
  • inert fillers such as for example barium sulphate, strontium sulphate
  • the hardening of the positive layer may be effected by the ordinary hardening agents, preferably formaldehyde. These hardening agents are applied in such quantities that the positive layer after storage for 8 days at 40 C. melts within 3 to minutes .when immersed in boiling water.
  • the SH-compounds referred to in our copending United States patent application Serial No. 730,259 are suitable as organic compounds for transforming the soluble silver halide complexes into diiiiculty soluble hydrophobic organic silver compounds, but especially suitable are organic mercapto compounds which contain alkyl or .alkenylradicals, having 8 to carbon atoms and which are soluble in aqueous liquids containing up to 20 percent of n-pr-opanol and being adjusted to a pH value of about 11-14 by means of alkaline metal hydroxides such as sodium or potassium hydroxide, Such compounds correspond for instance to the general formula:
  • Z represents one of the hetero atoms N and S which are present as ring elements of a heterocyclic compound selected from the group consisting of 5 and 6 membered hetcrocyclic compounds such as thiazoles, thiodiazoles, triazoles, imidazoles, pyrimidines.
  • R represents a normal or branched saturated or unsaturated aliphatic hydrocarbon radical with 8-20, preferably l220 carbon atoms, which is bonded directly or by means of additional linking members such as sulphur to one of the ring members of the heterocyclic compound.
  • additional linking members such as sulphur to one of the ring members of the heterocyclic compound.
  • R stands for a saturated or unsaturated aliphatic hydrocarbon radical having 8 to 20 carbon atoms, R for lower alkyl having 1 to 4 carbon atoms and Me for an alkali metal such as sodium or potassium.
  • Suitable compounds are by way of example:
  • the above mercapto compounds are usually applied in the form of 0.5-5 percent, preferably l3 percent, aqueous solutions being adjusted to a pH value of about 11-14 by means of alkali metal hydroxides such as sodium or potassium hydroxide.
  • alkali metal hydroxides such as sodium or potassium hydroxide.
  • these may have added organic solvents which are miscible with water such as acetone, methanol, ethanol, n-propanol, these solvents being applied in amounts of up to 20 percent by volume as calculated on the water applied.
  • Example 1 A paper sheet having wet-strength properties and weighing about 140 gJm. is coated in a first working step with a gelatine solution having the following composition:
  • gelatine layer is then treated with the following aqueous solution:
  • Example 2 The procedure is as in Example 1 with the variation that the positive after separation from the negative is treated with the solution of 10 g. of sodium dodecylxanthogenate, in 300 ml. of l N sodium hydroxide, and 300 ml. of water,
  • Example 3 The procedure is as in Example 1 with the variation that the positive after separation from the negative is treated with the solution of up to 200 prints are possible.
  • Example 4 The procedure is as in Example 1 with the variation that the positive after separation from the negative is treated with the solution of g. of 2-mercapto-5-dodecylmercapto-1,3,4-thiodiazole,
  • Example 5 The procedure is as in Example 1 with the variation that the positive after separation from the negative is treated with the solution of 6 g. of 2-mercapto-4-heptadecyl-thiazole, in 100 ml. of 1 N sodium hydroxide,
  • Example 6 The procedure is as in Example 1 with the variation that the positive after separation from the negative is treated with the solution of 6 g. of 1-amino-Z-mercapto-5-l1eptadecyl-1,3,4-triazole,
  • Example 7 The procedure is as in Example 1 with the variation that the positive after separation from the negative is treated with the solution of 6 g. of l-octyl-2-mercapto-benzimidazole, in 300 ml. of l N sodium hydroxide,
  • a process for the production of planographic printing forms which comprises exposing to an image a photographic silver halide emulsion in which at least 80% of the silver halide is silver chloride and the remaining silver halide is selected from the class consisting of silver chloride and silver bromide, contacting the exposed emulsion with a hardened gelatin layer containing alkaline earth thiosulphate, developing the exposed emulsion while in such contact with an alkaline aqueous silver halide developer to produce a negative of said image in the emulsion and to cause unexposed silver halide to dilluse into said gelatin layer as a silver complex, separating the emulsion from the gelatin layer, treating the resulting gelatin layer with an alkaline aqueous solution of a mercapto reactant selected from the class consisting of and S.Ra
  • Z represents a hetero atom selected from the class consisting of nitrogen and sulfur, said hetero atom and the N and C to which it is connected forming a heterocyclic ring selected from the class consisting of thiazol, thiodiazol, triazol, imidazol, benzimidazol and pyrimidine;
  • R and R stand for a member selected from the class consisting of an alkyl radical having 8-20 carbon atoms and mercapto alkyl, the alkyl group of which having 8-20 carbon atoms;
  • R stands for lower alkyl and Me stands for an alkali metal, to transform the silver complex into a hydrophibic silver compound of said reactant and thereby make a positive hydrophobic image of the object, and inking the resulting product with a greasy printing ink.
  • a process for the production of planographic printing forms which comprises exposing a silver halide emulsion layer to an object being reproduced, the emulsion containing at least one silver halide compound selected from the class consisting of silver chloride, silver chloride containing up to 5 percent silver iodide, silver bromide, silver bromide containing not more than 5 percent silver iodide, and mixtures thereof, developing said exposed silver halide emulsion layer to produce therein a negative silver image of the object to be reproduced, and treating said layer with a silver halide solvent to transform at least part of the silver halide of the unexposed areas of said emulsion layer into a water-soluble silver salt complex while in contact with a transfer layer of hardened gelatin devoid of silver salt precipitating agents, and transferring said soluble silver salt complex to said transfer layer to produce therein an invisible positive silver salt complex image of the object to be reproduced, separating the negative layer and said transfer layer from each other and thereafter treating said transfer layer with an alkaline
  • said colloid layer contains at least one compound selected from the group consisting of alkaline earth metal sulphates and thiosulphates.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US850769A 1958-11-07 1959-11-04 Photographic diffusion transfer process for planographic printing Expired - Lifetime US3063837A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA30693A DE1116536B (de) 1958-11-07 1958-11-07 Verfahren zur Herstellung von seitenrichtigen Flachdruckformen auf photographischem Wege nach dem Silbersalzdiffusionsverfahren

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US3063837A true US3063837A (en) 1962-11-13

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US (1) US3063837A (en(2012))
BE (1) BE584391A (en(2012))
CH (1) CH405931A (en(2012))
DE (1) DE1116536B (en(2012))
FR (1) FR1239847A (en(2012))
GB (1) GB883846A (en(2012))
NL (1) NL245101A (en(2012))

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3155514A (en) * 1961-12-08 1964-11-03 Du Pont Photographic compositions and elements
US3155517A (en) * 1962-11-08 1964-11-03 Du Pont Photographic compositions and elements
US3173789A (en) * 1962-01-29 1965-03-16 Eastman Kodak Co Method and composition for inhibiting silver sludge in thiosulfate monobaths
US3300306A (en) * 1957-10-25 1967-01-24 Gevaert Photo Prod Nv Process for the manufacture of printing plates
US3450535A (en) * 1962-01-25 1969-06-17 Lumoprint Zindler Kg Diffusion transfer receiving layer with high soda content
US3513251A (en) * 1969-04-07 1970-05-19 Southwire Co Multifilament conductor
US3819374A (en) * 1971-09-10 1974-06-25 Eastman Kodak Co Compositions for treating silver images

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4829723B1 (en(2012)) * 1970-12-29 1973-09-13

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1742710A (en) * 1928-03-29 1930-01-07 Henry L Krebs Process of transferring subjects to metal surfaces
GB648897A (en) * 1946-09-09 1951-01-17 Gevaert Photo Prod Nv Improvements in and relating to the production of planographic printing plates
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1742710A (en) * 1928-03-29 1930-01-07 Henry L Krebs Process of transferring subjects to metal surfaces
GB648897A (en) * 1946-09-09 1951-01-17 Gevaert Photo Prod Nv Improvements in and relating to the production of planographic printing plates
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300306A (en) * 1957-10-25 1967-01-24 Gevaert Photo Prod Nv Process for the manufacture of printing plates
US3155514A (en) * 1961-12-08 1964-11-03 Du Pont Photographic compositions and elements
US3155515A (en) * 1961-12-08 1964-11-03 Du Pont Photographic products
US3155507A (en) * 1961-12-08 1964-11-03 Du Pont Photographic processes
US3155516A (en) * 1961-12-08 1964-11-03 Du Pont Photographic products
US3450535A (en) * 1962-01-25 1969-06-17 Lumoprint Zindler Kg Diffusion transfer receiving layer with high soda content
US3173789A (en) * 1962-01-29 1965-03-16 Eastman Kodak Co Method and composition for inhibiting silver sludge in thiosulfate monobaths
US3155517A (en) * 1962-11-08 1964-11-03 Du Pont Photographic compositions and elements
US3513251A (en) * 1969-04-07 1970-05-19 Southwire Co Multifilament conductor
US3819374A (en) * 1971-09-10 1974-06-25 Eastman Kodak Co Compositions for treating silver images

Also Published As

Publication number Publication date
BE584391A (en(2012))
NL245101A (en(2012))
FR1239847A (fr) 1960-08-26
CH405931A (de) 1966-01-15
GB883846A (en) 1961-12-06
DE1116536B (de) 1961-11-02

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