US3007795A - Process for the production of laterally non-reversed positive copies by heat development - Google Patents

Process for the production of laterally non-reversed positive copies by heat development Download PDF

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Publication number
US3007795A
US3007795A US562613A US56261356A US3007795A US 3007795 A US3007795 A US 3007795A US 562613 A US562613 A US 562613A US 56261356 A US56261356 A US 56261356A US 3007795 A US3007795 A US 3007795A
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United States
Prior art keywords
silver halide
transfer layer
dye
transfer
layer
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Expired - Lifetime
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US562613A
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English (en)
Inventor
Haydn Hildegard
Konig Anita Von
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Agfa Gevaert NV
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Agfa AG
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Publication date
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142—Dye mordant

Definitions

  • the present invention relates to the production of laterally non-reversed positive copies by means of the known step of heat development of a silver halide layer, the developing operation being coupled with a transfer process.
  • the developer substance which is contained in a photographic silver halide emulsion layer and which has not been used up at the unexposed areas of said layer is transferred to a second layer which is in contact with the first layer and which contains one or more substances sensitive or insensitive to light which yield colored compounds with the said developer substance.
  • Aromatic diazo and nitroso compounds have been proposed as examples of reaction components in the positive layer.
  • heavy metal salts which can be used for the purpose of the invention are bichrornates, molybdates, tungstates, vanadates, uranates, titanates, niobates, and tantalates.
  • Preferably salts are used wherein the anions contain a heavy metal atom and the cations are either alkaline metals or NH
  • oxidizing agents there may be used all compounds which may be handled in the heat without hazard and which may be water-soluble or waterinsoluble, for instance perborates, arsenates, persulfates, chlorates, bromates, iodates and nitrates, preferably the alkali metal and kaline earth metal salts of said compounds.
  • the diazo compounds may be simple or stabilized compounds, for instance:
  • Quinone diazides such as diazo-Z-naphthol-4-sulphonic acid, diazo-Z-naphthol-6-bromo-4-sulphonic acid, diazosulphonates, such as 3-diazo-4-methoxy-6-benzoylaminotoluyl-sulfonate, 4-diazo-4'-methoxy-diphenylamino-sulfonate, 3 diazo 4 methoxy 6 benzoylaminotoluyl-finaphthalinsulfonate, diazoamino compounds, such as diazoamino compounds of diazotized anthranilic acid and ptoluidine, or diazoamine compounds of the sodium salt of diazotized 4-sulfoanthranilic acid and p-toluidine, furthermore, double salts of diazo compounds, such as double salts with the halides and sulfates of zinc, aluminum or magnesium as well as borontrifluoride and ary
  • the diazo compounds are added to the solution used for the preparation of the transfer layer preferably in concentrations of 0.52%.
  • the heavy metal salts are preferably applied in quantities of 540% as calculated on the Weight of diazo compounds used.
  • the oxidizing agent is preferably applied in a quantity of double to four times the weight of the heavy metal salt.
  • the reactivity is increased by adding acids or acid salts to the transfer layer.
  • the pH value of the solution used for the preparation of said layers shall be the lower, the higher the stabilization degree of the diazo compound. It is preferably adjusted between 2 and 7.
  • acids which are especially suitable for this purpose there may be mentioned sulfuric and phosphoric acid.
  • the acid is added in a quantity of about 20-100 ml. of H 50, (10%) per liter of transfer solution if for instance quinone diazides are used. If diazoamine compounds are used the solutions for the preparation of the transfer layer are gen erally kept neutral or weakly acid by addition of citric acid or acetic acid, or similar weak acids.
  • the negative layer For the preparation of the negative layer about 520 g., preferably 8-13 g. of developer substance are added to 1 liter of silver halide emulsion.
  • the emulsion is adjusted to a pH of about 4-7, preferably 5.6-6.3 by addition of alkali for instance sodium acetate, or acids, for instance citric acid.
  • alkali for instance sodium acetate
  • acids for instance citric acid.
  • the choice of the pH-value depends on the developer substance used and is lower with diamino or amino hydroxy compounds than with its dihydroxy compounds.
  • Any silver halide emulsion can be used as negative layer, such as for example silver chloride, silver bromide and silver iodide emulsions, if desired suitably mixed with one another, of high or low sensitivity, of soft, normal or steep gradation and also with normal, high or low silver content.
  • Suitable developer substances are the well known aromatic amino or hydroxy compounds or aminohydroxy compounds, with inclusion of amino or hydroxy compounds and aminohydroxy compounds of diphenylamine and diphenyl, e.g. 3-amino-4-oxydiphenyl, 2-amino-3-oxydiphenyl, 3-4-dioxydiphenyl, 3-4-dioxydiphenylamine, 2- amino-3-oxy-diphenylamine, 2amino 5 oxy-diphenylamine, 2-3-diaminodiphenylamine.
  • aminoand hydroxy compounds or aminohydroxy compounds of naphthalene which are substituted at the amino group by aliphatic, araliphatic or aromatic radicals or by sulphonic acid or SO R radicals, in which R stands for hydroxyl, alkyl, aryl or aralkyl.
  • R stands for hydroxyl, alkyl, aryl or aralkyl.
  • All film-forming colloids in general use for photographic purposes can be used as binding agents for the layers, for example, -gelatine, hydrophylic cellulose derivatives, such as partially hydrolysed acetyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone or mixtures of these substances.
  • Depth of color and shade of the image tone can be influenced by small additions of heavy metal salts, such as copper sulfate, zinc sulfate, ferric nitrate, chromium alum, cerium nitrate, uranium nitrate, Reinecke salt ((Cr(NH (SCN) ).NH .H O), and others.
  • the transfer paper can be coated on both sides, so that the positive paper can be arranged between two negative papers in the heat development, whereby a double-sided copy is obtained in a single operation.
  • the silver halide layer is exposed to an object to be reproduced and thereafter brought in contact with the transfer layer.
  • the combined layers are then heated for about 60 seconds to a temperature of about 50-180" C., preferably 80150 C., whereby the transfer layer may be heated to a somewhat lower temperature, such as 90-110 C., than the silver halide layer.
  • Hot presses, high glaze presses which can be heated electrically, drying drums and the like are suitable for carryingout the process. After separating the two layers a laterally correct color reproduction of the original to be reproduced is obtained.
  • Negative material 30 g. of 1-amino-2-naphthol, 30 g. of potassium-metabisulphite and 45 g. of acetic acid, are added to one liter of silver halide emulsion. Stabilizers and other conventional additives can be used. The emulsion is cast on a paper support and dried.
  • Positive layer 8 g. of diazotized 1-amino-2-naphthol-4-sulphonic acid, 0.4 g. of ammonium molybdate and 1.0 g. of sodium perborate are dissolved in 500 cc. of water.
  • 80 cc. of sulphuric acid, 500 cc. of 10% polyvinyl alcohol and 100 cc. of glycerine are then added to this solution. It is cast onto any suitable support such as paper and dried.
  • Positive material 10 g. of diazotized 1-amino-2-naphthol-4-sulphonic acid and 1 g. of potassium bichromate are dissolved in 500 cc. of water. 80 cc. of 10% sulphuric acid, 300 cc. of 10% aqueous polyvinyl alcohol and 100 cc. of glycerine are added to this solution. This is cast on a paper support and dried.
  • Negative material 30 g. of 1-methyl-sulphoamidonaphthol-Z, 30 g. of potassium metabisulphite, 40 g. of citric acid and 0.75 g. of benzotriazole are added to 1 litre of silver halide emulsion. This emulsion is coated on a support which is resistant to temperatures up to about 150 C., such as paper, and dried.
  • Example 1 A yellowish-brown image is obtained after processing as disclosed in Example 1.
  • Negative material 25 g. of 1-methylaminonaphthol-2, 30 g. of potassium metabisulphite, 30 g. of citric acid, and ml. of benzotriazole (5%) are added to one liter of silver halide emulsion. Other conventional additives can be used.
  • the emulsion is coated on a paper support and dried.
  • Negative material 8 g. of p-aminophenol hydrochloride, 10 g. of potassium meta-bisulphite and 150 g. of sodium acetate are dissolved in water and added to 1 liter of silver halide emulsion.
  • tabilizers and other conventional additives, for instance matting agents, can be used.
  • Negative material 20 g. of 4-isopropylidene-aminophenol are dissolved in some dimethyl-formamide and added to 1 liter of silver halide emulsion.
  • 10 g. of potassium metabisulphite, 150 g. of sodium acetate and 15 ml. of benzotriazole (5%) are then added. This emulsion is coated on a paper support and dried.
  • Positive material 10 g. of 4-diazo-4'-rnethoxydiphenylamine zinc chloride double salt, 0.7 g. of sodium molybdate, 2.5 g. of sodium bromate, 70 ml. of phosphoric acid (10%) and ml. of glycerine are added to 800 ml. of polyvinyl alcohol. The solution is cast on a paper support and dried.
  • the various formulations include hygroscopic ingredients (e.g. glycerine) that provide moisture which is recognized in the art as facilitating the transfer operation.
  • hygroscopic ingredients e.g. glycerine
  • the silver halide emulsion is a solidified form of a liquid having a pH between about 4 and 7
  • the developer is present in the emulsion in a proportion of between about 5 to 20 grams per liter
  • the transfer layer is a solidified form of a liquid having a pH of between about 2 and 7
  • the concentration of the diazo compound in the transfer layer is between about 0.5 to 2% by weight of the transfer layer
  • the concentration of the salt is about 5 to 10% by weight of the diazo compound.
  • a photographic transfer member having a support uniformly coated with a layer of a binding agent selected from the class consisting of gelatine, hydrophylic cellulose derivatives, polyvinyl alcohol, and polyvinyl pyrrolidone, said agent containing (1) a diazo compound that couples with a silver halide developer before the developer reacts with the silver halide to form a dye by such coupling, but after the developer reacts with the silver halide does not form a dye by such coupling, said developer being selected from the class consisting of aromatic amino, aromatic hydroxy and aromatic amino hydroxy compounds which undergo such coupling but which after developing a silver halide do not undergo such coupling; and (2) a salt of the class consisting of ammonium and alkali metal bichromates, molybdates, tungstates, vanadates, uranates, titanates, niobates and tantalates, copper sulfate, zinc sulfate, ferric nitrate, chromium alum, ce
  • a photographic transfer member having a support uniformly coated with a layer of a binding agent selected from the class consisting of gelatine, hydrophylic cellulose derivatives, polyvinyl alcohol, and polyvinyl pyrrolidone, said agent containing (1) a diazo compound that couples with a silver halide developer before the developer reacts with the silver halide to form a dye by such coupling, but after the developer reacts with the silver halide does not form a dye by such coupling, said developer being selected from the class consisting of mo matic amino, aromatic hydroxy and aromatic amino hydroxy compounds which undergo such coupling but which after developing a silver halide do not undergo such coupling; (2) a salt of the class consisting of ammonium and alkali metal bichromates, molybdates, tungstates, vanadates, uranates, titanates, niobates and tantalates, copper sulfate, zinc sulfate, ferric nitrate, chromium alum,

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US562613A 1955-02-11 1956-01-31 Process for the production of laterally non-reversed positive copies by heat development Expired - Lifetime US3007795A (en)

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US (1) US3007795A (en, 2012)
BE (1) BE545042A (en, 2012)
CH (1) CH347074A (en, 2012)
FR (1) FR1141235A (en, 2012)
GB (1) GB790811A (en, 2012)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3126281A (en) * 1959-02-04 1964-03-24 Formula
US3257205A (en) * 1960-10-12 1966-06-21 Gevaert Photo Prod Nv Method for heat development
US3408203A (en) * 1964-08-01 1968-10-29 Keuffel & Esser Co Diazotype reproduction materials containing an o-amino phenol as coupler
US3660093A (en) * 1968-07-08 1972-05-02 Agfa Gevaert Ag Dry azido thermal diffusion copying process

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1080854B (de) * 1957-12-10 1960-04-28 Zindler Lumoprint Kg Verfahren zur Herstellung seitenrichtiger positiver Abbildungen unter Waermeeinwirkung und Positivmaterial zur Durchfuehrung dieses Verfahrens
US3033677A (en) * 1959-06-19 1962-05-08 Eastman Kodak Co Photographic processes utilizing photolytic halogen
US4021240A (en) 1975-12-22 1977-05-03 Eastman Kodak Company Photothermographic and thermographic compositions and uses therefor containing sulfonamidophenol reducing agents and four equivalent color couplers
US4187108A (en) * 1977-02-07 1980-02-05 Eastman Kodak Company Heat developable material and process
CA1085666A (en) * 1977-02-07 1980-09-16 Eastman Kodak Company Photographic material having a heat developable layer and a layer containing an azoaniline dye

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1920542A (en) * 1930-09-04 1933-08-01 Gen Aniline Works Inc New dyeing preparation and its conversion to dyestuffs
US1922727A (en) * 1928-09-29 1933-08-15 Celanese Corp Production of pattern effects upon textile fabrics or other materials
US1964358A (en) * 1931-10-19 1934-06-26 Kalle & Co Ag Light-sensitive layers containing a titanium salt of an organic hydroxy acid and process of preparing them
US2066918A (en) * 1931-09-21 1937-01-05 Light-sensitive material and a proc
US2113944A (en) * 1933-09-11 1938-04-12 Dietzgen Eugene Co Production of photographic diazotype prints
US2217189A (en) * 1938-12-05 1940-10-08 Kalle & Co Ag Process of preparing photographic prints
US2228562A (en) * 1938-03-17 1941-01-14 Dietzgen Co Eugene Production of photographic diazotype prints
GB629656A (en) * 1946-09-12 1949-09-26 Gen Aniline & Film Corp Process for positive diazo-type and negative metal reproduction images and light-sensitive material therefor
US2661293A (en) * 1946-10-08 1953-12-01 Polaroid Corp Process of producing a colored photographic image by means of exhaustion of developer
US2747999A (en) * 1953-03-16 1956-05-29 Eastman Kodak Co Photographic reproduction process

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1922727A (en) * 1928-09-29 1933-08-15 Celanese Corp Production of pattern effects upon textile fabrics or other materials
US1920542A (en) * 1930-09-04 1933-08-01 Gen Aniline Works Inc New dyeing preparation and its conversion to dyestuffs
US2066918A (en) * 1931-09-21 1937-01-05 Light-sensitive material and a proc
US1964358A (en) * 1931-10-19 1934-06-26 Kalle & Co Ag Light-sensitive layers containing a titanium salt of an organic hydroxy acid and process of preparing them
US2113944A (en) * 1933-09-11 1938-04-12 Dietzgen Eugene Co Production of photographic diazotype prints
US2228562A (en) * 1938-03-17 1941-01-14 Dietzgen Co Eugene Production of photographic diazotype prints
US2217189A (en) * 1938-12-05 1940-10-08 Kalle & Co Ag Process of preparing photographic prints
GB629656A (en) * 1946-09-12 1949-09-26 Gen Aniline & Film Corp Process for positive diazo-type and negative metal reproduction images and light-sensitive material therefor
US2661293A (en) * 1946-10-08 1953-12-01 Polaroid Corp Process of producing a colored photographic image by means of exhaustion of developer
US2747999A (en) * 1953-03-16 1956-05-29 Eastman Kodak Co Photographic reproduction process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3126281A (en) * 1959-02-04 1964-03-24 Formula
US3257205A (en) * 1960-10-12 1966-06-21 Gevaert Photo Prod Nv Method for heat development
US3408203A (en) * 1964-08-01 1968-10-29 Keuffel & Esser Co Diazotype reproduction materials containing an o-amino phenol as coupler
US3660093A (en) * 1968-07-08 1972-05-02 Agfa Gevaert Ag Dry azido thermal diffusion copying process

Also Published As

Publication number Publication date
BE545042A (en, 2012)
FR1141235A (fr) 1957-08-28
GB790811A (en) 1958-02-19
CH347074A (de) 1960-06-15

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