US3436217A - Highly sensitive direct positive photographic material with extremely steep gradation - Google Patents

Highly sensitive direct positive photographic material with extremely steep gradation Download PDF

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Publication number
US3436217A
US3436217A US354773A US3436217DA US3436217A US 3436217 A US3436217 A US 3436217A US 354773 A US354773 A US 354773A US 3436217D A US3436217D A US 3436217DA US 3436217 A US3436217 A US 3436217A
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United States
Prior art keywords
layer
silver
emulsion
light
sensitive
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Expired - Lifetime
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US354773A
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English (en)
Inventor
Walter Kleist
Franz Moll
Peter Kruck
Ehrhard Hellmig
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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
    • 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
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer
    • 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
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/26—Image-receiving layers
    • G03C8/28—Image-receiving layers containing development nuclei or compounds forming such nuclei

Definitions

  • This invention relates to a three-layer photographic material for the production of direct positive images with extremely steep gradation by the silver salt diffusion process.
  • direct positive films can be based on various principles, for example on the Herschel effect. Films of this type consist of chemically dogged or pre-exposed silver halide emulsions, which produce a positive image by a subsequent image-wise exposure with red or infrared light.
  • the phenomenon which is known as solarisation can be used for the production of positive images.
  • Another photographic effect which is known as the Villard effect can likewise serve *for the production of direct positive images.
  • the light-sensitive photographic layers are pro-exposed wit-h X-rays and subsequently exposed with normal light to form an image.
  • Positive images can be produced in a relatively simple manner by the so-called silver salt diffusion process.
  • a negative paper with a light-sensitive layer is employed together with a transfer material which contains a layer with reducing agents or development nuclei.
  • These layers are processed by both layers being developed in contact with one another in the presence of silver salt solvents.
  • the undeveloped silver salt of the emulsion layer is dissolved in complex form and diffuses into the image-receiving or transfer layer, where it is deposited on the development nuclei.
  • Processes for silver salt diffusion have also been proposed in which a twolayer material is employed. In this case, the so-called nucleus layer and the light-sensitive layer containing the 3,436,217 Patented Apr. 1, 1969 ice silver halide are cast one above the other.
  • the light-sensitive emulsion layer is rinsed 011.
  • gradation is meant the characteristic curve or H and D-curve of an emulsion.
  • H and D-curve the characteristic curve or H and D-curve of an emulsion.
  • Support-For this purpose conventional transparent or opaque materials can be used, such as paper, cellulose ester, polystyrene polycarbonates, especially of bis-phenylol alkanes, or polyesters particularly those of ethylene glycol and terephthalic acid.
  • the support can, if desired, be provided in the usual way with a subbing layer.
  • the layer containing the silver-precipitating de velopment nuclei is coated on the support.
  • Suitable nuclei are, for example, colloidally dispersed noble metals, such as silver, gold, etc., or sulfides or selenides of various metals, e.g., of silver, zinc, cadmium or sodium. Gelatine is used as the layer-forming binding agent.
  • the layer thickness should :be between 0.5 and 3 advantageously l2
  • the concentration of the nuclei, for example of silver sulfide should correspond to 0.8-2 mg, advantageously about 1.2-1.6 mg, of silver per square meter.
  • blue toners are added, which are known per se, for example, imidazoles, triazoles, tetrazoles, preferably those with mercapto groups like phenyl mercaptotetrazole.
  • Suitable compounds are disclosed in German Patents Nos. 887,733, 890,755; German Auslegeschrift 1,062,112, 1,064,807, 1,070,029, 1,153,247; French Patent No. 1,140,526; British Patent Nos. 706,333, 922,479; U.S. Patent No. 2,704,721 and Belgian Patents Nos. 542,151 and 574,756.
  • quaternary ammonium salts and thioethers It is also possible to employ for this purpose quaternary ammonium salts and thioethers.
  • the nucleus layer is well hardened in the usual way, for example, by the addition of formalin, mucochloric acid or glyoxal, so that its softening or melting point lies 3 above 100 C. preferably between 100 and 120 C. No softening of the layer should occur below 100" C.
  • an intermediate layer of gelatine Onto this nucleus layer is cast an intermediate layer of gelatine, which likewise is hardened in the same manner.
  • the thickness of this layer should amount to approximately /3 up to at most 3 times the thickness of the nucleus layer and it is provided to facilitate the Washing away of the emulsion layer which is necessary during the processing, and more especially to protect the silver image in the nucleus layer from mechanical damage. It is preferred to use intermediate layers which are of the same thickness as the nucleus layer, or thinner than it by approximately the factor 0.3.
  • the light-sensitive gelatino-silver halide emulsion is applied as the uppermost layer, the light-sensitive silver halide containing 1040 mol percent of silver bromide and 90-60 mol percent of silver chloride, advantageously of 2035 mol percent of silver bromide and 65-80% of silver chloride.
  • Preferred are emulsions, which are slightly fogged.
  • Particularly suitable are emulsions uniformly fogged to a degree that they yield a silver density of about 0.30.5 when developed with the following developer at 20 C. for 3 minutes:
  • the emulsions can be prepared by known processes. They are rinsed and ripened up to maximum sensitivity. In order to produce an increased sensitivity, the emulsion may contain sulphur sensitizers, for example, thiosulphate or thiourea, or reduction sensitizers, such as tin salts. Noble metals, such as gold, palladium, ruthenium, rhodium and iridium, can also be added. The emulsion may further contain other chemical sensitizers, such as onium salts, e.g. ammonium, sulphonium and phosphonium salts, as well as polyethylene oxides. Optical sensitization is effected with known sensitizing dyes such as cyanines and merocyanines.
  • sulphur sensitizers for example, thiosulphate or thiourea
  • reduction sensitizers such as tin salts.
  • Noble metals such as gold, palladium, ruthenium
  • the emulsion layer is not hardened.
  • primary amino compounds which are photographically inert and which are capable of preventing the hardening of the gelatine layer by aldehyde compounds,
  • degraded gelatine natural gelatin which has been treated with acids or alkalis and which has an average molecular weight of between some hundreds and 10,000.
  • the hardening can also be largely prevented by adjusting the pH value of the emulsion to a value between 3 and 5, advantageously 3.5 to 4.5.
  • the light-sensitive layer has a softening or melting point of between 30 and 50 C.
  • dek velopers suitable as developers, it being necessary for these dek velopers to contain a solvent for the silver halide, e.g., sodium thiosulphate or sodium sulphite, in quantities of about 10-20 g./1.
  • a solvent for the silver halide e.g., sodium thiosulphate or sodium sulphite
  • the materials are processed in known manner and the unhardened negative layer, after exposure and development, is rinsed off with warm water having a temperature of between 30 and C.
  • Example 1 A fine-grain gelatino-silver chlorobromide emulsion with 30 mol percent of bromide and mol percent of chloride and a content of 1.5 g. of urea per kg. of emulsion ready for casting, is produced by the usual methods (see, for example, P. Glafkides Photographic Chemistry, vol. I, Fountain Press, London, 1958), washed and ripened up to maximum sensitivity. The ratio between silver and gelatine is 1:1. If the emulsion is cast on to a conventional support casting thickness about 8 exposed and developed, it yields a 7 value of 4.1 after 3 minutes of developing the the following developer:
  • the same emulsion is applied with a thickness of about 5, onto a hardened gelatine layer with a thickness of about 0.5 which had been coated on a supported hardened gelatine layer containing development nuclei consisting of Ag S and blue toners in a layer thickness of about la.
  • the resulting photographic element is exposed and developed for 3 minutes in a developer with the composition as indicated below. After washing off the emulsion layer with warm water, a 7 value higher than 15 is obtained in the hardened gelatine layer which had contained the development nuclei, with a fogging value of 0.07, the maximum density being higher than 3.
  • the developer has the following composition:
  • Example 2 A gelatino-silver chlorobrornide emulsion the silver halide of which consists of 20 mol percent of bromide and 80 mol percent of chloride and which contains 1.5 g. of urea per kg. is prepared as indicated in Example 1. That emulsion is applied onto the hardened gelatine layer of a multilayer element consisting of the hardened gelatin layer coated on another hardened gelatin layer which contains development nuclei consisting of silver and blue toners.
  • the film is exposed and developed for 3 minutes in the second mentioned developer of Example 1 and the emulsion layer is rinsed oif.
  • the resulting silver image has a value of about 15, the maximum density being higher than 3.
  • the fogging value is 0.07.
  • Example 2 The silver halide emulsion of Example 2 which contains 20 mol percent of silver bromide is half as sensitive as the emulsion of Example 1.
  • Example 3 The light-sensitive three layer photographic element is produced as described in Examples 1 and 2, the silver halide of the light-sensitive layer consisting of of silver chloride and of silver bromide. The film is exposed and developed for 3 minutes in the second mentioned developer of Example 1. Thereafter the emulsion layer is washed oiT. The resulting silver image in the layer which had contained the development nuclei has a 7 value of 12, the maximum density being higher than 3.
  • the photographic material of Example 1 is 4 times as sensitive as the material of this example.
  • the fogging of the material of the present example is 0.06.
  • a light-sensitive photographic element consisting essentially of (I) an unhardened silver halide gelatin emulsion layer having a softening point of between 30 and 50 C. and a pH-value of between 3 and 5, the silver halide of which consist of 1 0-40 mol percent of silver bromide and 90-60 mol percent of silver chloride, the emulsion layer additionally containing a compound having a primary amino group capable of preventing hardening of the gelatin in the layer, the emulsion layer being coated on an (II) intermediate layer consisting essentially of hardened gelatin, superimposed on a (III) nucleus layer the binding agent of which consists essentially of hardened gelatin having a softening point of above 100 C., the thickness of the nucleus layer being 0.5-3 microns and between /a to 3 times the thickness of the intermediate layer, the nucleus layer containing blue toner and development nuclei in an amount corresponding to 0.8-2 mg. silver per square meter, the nucleus layer
  • a process for the production of direct positive photographic images of exteremely high contrast comprising the steps of (a) exposing an object to be reproduced to a light-sensitive photographic element which consists of (I) an unhardened silver halide gelatin emulsion layer having a softening point of between 30 and 50 C. and a pH-value of between 3 and 5,
  • the silver halide of which consists of 10-40 mol percent of silver bromide and -60 mol percent of silver chloride said emulsion layer additionally containing a compound having a primary amino group capable of preventing hardening of the gelatin in the layer, the emulsion layer being coated on an (II) intermediate layer consisting essentially of hardened gelatin, superimposed on a (III) nucleus layer the binding agent of which consists essentially of hardened gelatin having a softening point of above C., the thickness of the nucleus layer being 0.5-3 microns and between /3 to 3 times the thickness of the intermediate layer, the nucleus layer containing blue toner and development nuclei in an amount corresponding to 08-2 mg. silver per square meter, the nucleus layer being coated on (IV) a sheetlike support,
  • nucleus layer of the light-sensitive photographic element contains development nuclei in an amount corresponding to 1.2-1.6 mg. silver per square meter and l-phenylmercapto tetrazole as blue toner in an amount of between 13-20 g. per g. of silver.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US354773A 1963-04-09 1964-03-25 Highly sensitive direct positive photographic material with extremely steep gradation Expired - Lifetime US3436217A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA42845A DE1175078B (de) 1963-04-09 1963-04-09 Lichtempfindliches photographisches Direkt-positivmaterial mit extrem steiler Gradation fuer das Silbersalzdiffusionsverfahren

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US (1) US3436217A (enrdf_load_stackoverflow)
BE (1) BE646310A (enrdf_load_stackoverflow)
CH (1) CH449420A (enrdf_load_stackoverflow)
DE (1) DE1175078B (enrdf_load_stackoverflow)
GB (1) GB1053074A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302526A (en) * 1978-11-11 1981-11-24 Mitsubishi Paper Mills, Ltd. Materials for silver complex diffusion transfer process
US5196290A (en) * 1991-06-20 1993-03-23 Agfa-Gevaert, N.V. Method for making a lithographic aluminium offset printing plate by the silver salt diffusion transfer process

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043244A (en) * 1990-09-10 1991-08-27 E. I. Du Pont De Nemours And Company Process for defined etching of substrates

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635048A (en) * 1948-07-06 1953-04-14 Polaroid Corp Photographic transfer product and process
US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process
US3311473A (en) * 1962-06-28 1967-03-28 Eastman Kodak Co Silver halide diffusion process and products therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635048A (en) * 1948-07-06 1953-04-14 Polaroid Corp Photographic transfer product and process
US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process
US3311473A (en) * 1962-06-28 1967-03-28 Eastman Kodak Co Silver halide diffusion process and products therefor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302526A (en) * 1978-11-11 1981-11-24 Mitsubishi Paper Mills, Ltd. Materials for silver complex diffusion transfer process
US5196290A (en) * 1991-06-20 1993-03-23 Agfa-Gevaert, N.V. Method for making a lithographic aluminium offset printing plate by the silver salt diffusion transfer process

Also Published As

Publication number Publication date
CH449420A (de) 1967-12-31
BE646310A (enrdf_load_stackoverflow) 1964-10-09
DE1175078B (de) 1964-07-30
GB1053074A (enrdf_load_stackoverflow)

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