Classifications

• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
  • G03C2007/3034—Unit layer
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group

Definitions

• the invention relates to a photographic recording material with increased sensitivity, improved graininess and improved behavior when overexposed.
• German Offenlegungsschrift 1 522 376 and GB-PS 1 145 753 discloses color photographic recording materials with a silver halide emulsion layer which has at least two individual layers sensitive in the same spectral range, one of which is relatively sensitive and contains a fast coupler and a slow coupler and of which the other single layer is relatively insensitive and contains a slow coupler.
• the material can additionally contain a DIR coupler and should have a higher sensitivity with an improved graininess.
• a process for the production of color images is known from German Offenlegungsschrift 2,650,764, in which the exposed photographic recording material is developed in the presence of certain polyfunctional couplers and certain polyfunctional developer compounds to form dyes of a neutral black color.
• a black-and-white photographic material is known from German Offenlegungsschrift 2,038,199 and US Pat. No. 3,695,882, in which at least two silver halide emulsions containing one or more color couplers are applied to a support and each silver halide emulsion is spectrally too practical same area is sensitized.
• the object of the invention is to provide an improved photographic material.
• this material is said to ensure better graininess and greater exposure latitude.
• a photographic recording material which has at least two panchromatically sensitized silver halide emulsion layers of different sensitivity, of which the more sensitive silver halide emulsion layer is arranged farther from the support than the less sensitive one, and in each of these two layers at least two color couplers are contained, at least one of which is at Chromogenic development forms a yellow dye, characterized in that at least one layer contains a compound which releases a development inhibitor and in that a yellow coupler is contained in the more sensitive silver halide emulsion layer in a relatively quickly coupling form and in the less sensitive layer a yellow coupler is contained in a relatively slow coupling form.
• the material according to the invention preferably has two silver halide emulsion layers, both of which are panchromatically sensitized and which contain magenta and cyan couplers in addition to the yellow couplers.
• this material is chromogenically developed after imagewise exposure, a black and white image is generally obtained.
• the fast-coupling yellow coupler in the more sensitive layer is a hydrophilic, alkaline-dissolved coupler.
• a hydrophobic, emulsified yellow coupler is preferably present in the less sensitive layer.
• all couplers can also be emulsified.
• the more sensitive Emul sion layer in addition to the relatively quickly coupling yellow coupler, there is also a relatively slowly coupling yellow coupler.
• a yellow coupler that couples relatively quickly can also be present.
• the molar ratio of the fast-coupling to the slowly-coupling yellow coupler is preferably between 10 and 0.8 in the more sensitive layer and preferably between 0.2 and 1.3 in the less sensitive layer.
• the cyan and magenta couplers contained in the more sensitive layer are preferably slow-coupling couplers, in particular hydrophobic, emulsified couplers.
• the compound that cleaves a development inhibitor is, in particular, a DIR compound that is preferably contained in at least two silver halide emulsion layers.
• the materials according to the invention are advantageously suitable for producing photographic images by imagewise exposure and development.
• the usual color developer substances are particularly suitable for development.
• the materials according to the invention are particularly suitable as recording materials for the production of Negatives, of which copies can be made in a known manner.
• the copies can be made on customary, color coupler-free black and white materials or on the materials according to the invention.
• As a result of the extraordinarily good fine-grained and tonal correctness with the highest sensitivity of the recording materials according to the invention surprisingly fine-grained and tonally correct copies can also be obtained in this way. While the graininess increases with density in conventional materials, a decrease in graininess with color density is achieved with the materials according to the invention.
• the silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide. Bromide and bromide iodide emulsions are preferably used.
• the more sensitive silver halide emulsion is preferably a silver bromide iodide emulsion with more than 5% iodide and the less sensitive emulsion is preferably a silver bromide iodide emulsion with less than 5 mol% iodide.
• the ratio of the sensitivity between the more sensitive and the comparatively less sensitive silver halide emulsion is preferably between 1: 3 and 1:20, in particular between 1: 5 and 1:10.
• the color couplers used can in principle be any type of non-diffusing compound from which image dyes can be produced with suitable treatment (development). Common, non-diffusing colors are preferred couplers used, which react in a known manner with the color developer oxidation products to form a non-diffusing dye.
• a color coupler with an open-chain ketomethylene group is generally used to produce the yellow partial color image
• a coupler of the phenol or Cc-naphthol type is usually used to produce a blue-green partial color image
• a color coupler of the 5-pyrazolone or type type is usually used to produce the purple partial color image Indazolons used. Color couplers of these types are known in large numbers and are described in a large number of patents.
• the color couplers can be either conventional 4-equivalent couplers or 2-equivalent couplers, in which a smaller amount of silver halide is required to produce the color.
• 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
• the fast or slow yellow couplers to be used according to the invention differ in their relative coupling speed, that according to known ones Methods can be determined (see, for example, "Information from the research laboratories of Agfa Leverkusen / Kunststoff", Volume III, page 81 and according to the one in German Offenlegungsschrift 2 853 362, pages 12 to 16).
• the coupling speed of the fast coupling color coupler is preferably 3 to 50, preferably 4 to 12 times greater than that of the slow color coupler. It should be noted here that the reactivity of couplers depends not only on the structure of the coupler in question but also on the method used for incorporation into the photographic material.
• Couplers with a relatively high or relatively low coupling speed are known, for example, from German Offenlegungsschrift 1 958 709, pages 6 to 11 and German Offenlegungsschrift 2 600 524, pages 8 to 21.
• 0.03 to 0.5 mol are used per mole of silver halide the yellow coupler is used.
• Purple couplers and cyan couplers are preferably added in an amount such that a neutral gray image is obtained after imagewise exposure and development.
• the photographic materials also contain compounds which react with color developer oxidation products and thereby release a substance which inhibits the development of the silver halide.
• These compounds can be contained in one but also in at least 2 panchromatically sensitized layers.
• DIR development inhibitor releasing
• DIR couplers which are color couplers which contain a detachable inhibitor residue in the coupling point.
• DIR couplers are described, for example, in US Pat. No. 3,227,554.
• Another group of compounds which release development-inhibiting substances upon reaction with color developer oxidation products is described in US Pat. No. 3,632,345. These are not color couplers. Accordingly, no dyes are produced when the development-inhibiting substances are released.
• this group of compounds is also referred to as colorless coupling DIR couplers or as DIR compounds.
• the amount of DIR coupler or DIR compound used is preferably between 2 mg and 20 mg per g A G NO 3 of the silver halide emulsion.
• the effective reaction rate constants in the relatively sensitive silver halide emulsion layer determined according to German Offenlegungsschrift 2,853,362 are preferably above 50,000 for the yellow coupler and preferably between 2,000 and 10,000 for the magenta and cyan couplers.
• the reaction rate constant of the yellow coupler in the less sensitive layer is preferably between 2,000 and 10000.
• the reaction rate constant of the magenta and cyan couplers of the less sensitive layer is above 1000.
• the reaction rate constant of the DIR couplers used is preferably 3,000-50,000 (the dimension of the reaction rate constant is: lmol -1 xsec -1 ). If all yellow couplers are emulsified, the speed constant of the relatively quickly coupling yellow coupler is preferably above 5000 and that of the relatively slowly coupling coupler is preferably below 3000.
• Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
• the emulsions can also be chemically sensitized, for example by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea and sodium thiosulfate.
• Reducing agents for example those in the Belgian patent, can also be used as chemical sensitizers Writ 493 464 or 568 687, described tin compounds, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, for example according to the Belgian patent 547 323, can be used.
• Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers.
• polyalkylene oxide derivatives for example with polyethylene oxide having a molecular weight between 1000 and 20,000, and also with condensation products of alkylene oxides and alcohols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
• the emulsions are panchromatic sensitized, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines and dicarbocyanines, rhodacyanines and the like.
• polymethine dyes such as neutrocyanines, basic or acidic carbocyanines and dicarbocyanines, rhodacyanines and the like.
• Such sensitizers are in the work of F.M. Hamer "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, page 433.
• Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are, for example, in the article by Birr, Z.Wiss.Phot. 47 (1952), 2 to 58.
• Other suitable stabilizers include heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
• the layers of the photographic material can be hardened in the usual manner, for example with formaldehyde, with hardeners of the epoxy type, the heterocyclic ethyleneimine and the acryloyl type.
• the material according to the invention can be developed using the customary black and white developers, but is preferably subjected to color development, in particular color negative development. Reverse processing is also possible.
• color development in particular color negative development.
• Reverse processing is also possible.
• the couplers contained in the material react with the oxidation product of the color developer substance used.
• Suitable color developer substances are in particular of the p-phenylenediamine type, for example: N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 2-amino-5-diethylamino-toluene, N-butyl -N- LU -sulfobutyl-p-phenylenediamine, 2-amino-5- (n-ethyl-N-ß-methanesulfonamidethyl-amino) -toluene, N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine, N, N -Bis- (ß-hydroxyethyl) -p-phenylenediamine, 2-amino-5- (N-ethyl-N-ß-hydroxyethylamino) toluene.
• Further useful color developers are described,
• the material After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
• the usual compounds can be used as bleaching agents, e.g. Ferricyanides, dichromates, water-soluble cobalt complexes etc.
• Iron-III complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, etc.
• the materials according to the invention are versatile. They are suitable for highly sensitive camera films, but can also be used for reproduction photography to produce color separations.
• the material according to the invention if it is subjected to a conventional color negative treatment, the silver image can be completely removed during the bleaching stage, since the image formed by the color couplers remains. In this way, in contrast to conventional SW materials, the silver can be largely recycled.
• the material according to the invention surprisingly has two opposing but desirable properties, namely the ability to achieve the highest sensitivity with the finest grain.
• the relatively low-sensitivity emulsion thus obtained is poured onto a transparent support.
• a relatively low-sensitivity emulsion is prepared as described under A), but with the following differences: Instead of the soluble purple coupler of formula 2, the hydrophobic purple coupler of formula 7 is emulsified in the manner described for the yellow coupler of formula 1 and enough emulsifier is added that 30 g of the coupler are present. Analogously, an emulsion of the cyan coupler of formula 8 is added. The relatively low-sensitivity emulsion obtained in this way is poured onto a transparent support. A highly sensitive layer is then cast over this layer, which was produced as follows:
• Coupler emulgate is added to 1000 g of a panchromatically sensitized, highly sensitive silver bromide emulsion with 6% iodide, which according to the method described under A) were prepared in such amounts that 12 g of the yellow coupler of formula 1, 10 g of the magenta coupler of formula 7 and 10 g of the cyan coupler of formula 8 are present.
• the material A) according to the invention and the comparison material B) are exposed imagewise and color developed according to the method described by P. Glafkides, Chimie et Physique Photographiques, Paris 1976 on page 748 as "C 41 process".
• the structure A) according to the invention has a 60% higher sensitivity of the yellow extract than the structure B) with the same course of the density curves in yellow, purple and teal.
• the sharpness of the image recording is improved according to the invention.
• the modulation transmission has already dropped to 50% of the value for one line per mm at 27 lines / mm, this only occurs for material A) according to the invention at 31 lines per mm.
• the low-sensitivity emulsion thus produced is poured onto a transparent support.
• a coupler-containing photosensitive emulsion which was prepared as described under A), is poured onto a transparent support, with the difference that no DIR compound is added.
• a second, highly sensitive emulsion layer is poured onto this layer, which is produced according to the following recipe.
• Example 1 The materials A) and B) are processed as indicated in Example 1. With an otherwise identical course of the density curves in yellow, purple and blue-green, the structure A) according to the invention shows a sensitivity which is 40% higher than that of the comparison structure B).
• Example 2A The material according to the invention specified in Example 2A is exposed imagewise and developed in a color developer.
• a highly sensitive and commercially available black and white film based on silver halide with a corresponding sensitivity to light (27 DIN), which has no color kuppler contains, imagewise exposed and in the Glafkides, loc. cit. P. 90 software developer described as DK 60a.
• the development of both materials was carried out so that the same gradation was obtained.
• the granularity of the films obtained is given in the following table:
• the material according to the invention gives a significantly improved granularity.
• the purple coupler of formula 7 and the cyan coupler of formula 8 are dispersed accordingly. So much of both coupler emulsifiers is added that 30 g of the coupler in question are present. 60 ml of a 2% strength solution of the DIR compound of the formula 4 are then added.
• the low-sensitive emulsion thus produced is poured onto a transparent support.
• a material similar to that indicated in Example 4 is produced, with the modification that a coupler emulsate which contains 5 g of the yellow coupler of the formula A and 5 g of the yellow coupler of the formula B instead of the amount given in example 4 is added to the low-sensitivity silver halide emulsion . Furthermore, 2 g of the yellow coupler of formula A and 2 g of the yellow coupler of formula B were added to the more sensitive silver bromide emulsion.

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• 1980
  • 1980-08-01 DE DE19803029209 patent/DE3029209A1/de not_active Withdrawn
• 1981
  • 1981-07-20 EP EP81105678A patent/EP0045427B1/fr not_active Expired
  • 1981-07-20 DE DE8181105678T patent/DE3164155D1/de not_active Expired
  • 1981-07-23 US US06/286,261 patent/US4348474A/en not_active Expired - Fee Related
  • 1981-07-30 CA CA000382847A patent/CA1153239A/fr not_active Expired
  • 1981-07-31 JP JP56119386A patent/JPS5758147A/ja active Pending

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