EP0329016B1 - Matériau de reproduction photographique couleur - Google Patents

Matériau de reproduction photographique couleur Download PDF

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Publication number
EP0329016B1
EP0329016B1 EP89102221A EP89102221A EP0329016B1 EP 0329016 B1 EP0329016 B1 EP 0329016B1 EP 89102221 A EP89102221 A EP 89102221A EP 89102221 A EP89102221 A EP 89102221A EP 0329016 B1 EP0329016 B1 EP 0329016B1
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EP
European Patent Office
Prior art keywords
couplers
layer
colour
dir
coupler
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EP89102221A
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German (de)
English (en)
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EP0329016A2 (fr
EP0329016A3 (en
Inventor
Reinhart Dr. Matejec
Dirk Dr. Hübner
Franz Dr. Moll
Heinrich Dr. Odenwälder
Erich Dr. Wolff
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Agfa Gevaert AG
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Agfa Gevaert 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
    • 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
    • G03C7/32—Colour coupling substances
    • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
    • 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
    • G03C2200/00—Details
    • G03C2200/52—Rapid processing
    • 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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density
    • 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
    • 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
    • G03C7/32—Colour coupling substances

Definitions

  • the invention relates to a color photographic recording material, the sensiometric data (e.g. sensitivity, gradation and fog) are influenced by fluctuations in the processing conditions (e.g. duration, temperature, pH of the developer, concentration of the developer, etc.) significantly less than conventional material.
  • the processing conditions e.g. duration, temperature, pH of the developer, concentration of the developer, etc.
  • the invention is based on the object of developing a color photographic recording material which, with very good and constant color reproduction, is less susceptible to fluctuations during processing, particularly with regard to shorter process times.
  • the relative maximum color density should preferably be 70%.
  • the silver halide emulsions used in the material according to the invention must therefore develop very quickly.
  • the inhibitors split off from the DIR coupler should preferably have a diffusibility of ⁇ 0.4.
  • the diffusibility is a measure of the distance covered by the inhibitor after the cleavage during the coupling process of the DIR coupler within the emulsion layers, on which it develops its inhibitory effect.
  • the color photographic recording material contains in particular at least one blue-sensitive silver halide emulsion layer to which a yellow coupler is assigned, at least one green-sensitive silver halide emulsion layer to which a magenta coupler is assigned and at least one red-sensitive silver halide emulsion layer to which a cyan coupler is associated, preferably at least one layer for each spectral range corresponding to the conditions according to the invention.
  • the color couplers of the higher sensitive sub-layers preferably have an even higher coupling rate constant than that of the lower sensitive sub-layers (cf. DE-OS-1 958 709).
  • mixtures of several rapidly developing emulsions and / or mixtures of several rapidly coupling color couplers and / or mixtures of several fast coupling DIR couplers, the inhibitors of which have high diffusibility can also be used in the partial layers of the material according to the invention.
  • amines such as p-chlorobenzylamine, ⁇ - (p-chlorophenyl) ethylamine, p-nitrobenzylamine, ⁇ -phenoxyethylamine, ⁇ -4-bromophenoxyethylamine, ⁇ -4-chlorophenoxypropylamine or 2-aminomethylthiophene, furfurylamine, 5-aminomethylamine 1-methyl-4-imidazolone reached.
  • thioethers can also be used as development accelerators.
  • the silver halide emulsions according to the invention can e.g. by single entry, double entry, continuous precipitation, accelerated precipitation or interrupted precipitation in the presence of a hydrophilic colloid, e.g. Gelatin, which is also modified, e.g. can be prepared by reaction with phthalic anhydride, or modified or also oxidized in molecular weight (P. Glafkides, Chimie et Physique Photographiques, P. Montel Paris (1967); GF Duffin Photographic Emulsion Chemistry, The Focal Press London (1966); Research Disclosure (1983) No. 225, 22534). Furthermore, the method of ultrafiltration can be used to separate off the alkali metal nitrates released during the silver halide precipitation.
  • the silver halide can be precipitated at pH values between 2-8.
  • the pAg values can range between 6 and 10. These values can change continuously during the felling process; however, they can also be kept constant during the precipitation.
  • the halides used can consist of silver bromide, silver bromide chloride, silver bromide iodide and silver chloride bromide iodide, the total iodide content being ⁇ 15 mol%, preferably ⁇ 10 mol% and depending on the type of developer, e.g. is the content of silver halide solvent in the developer, and the position of the emulsion in the layer structure.
  • the iodide content of the bottom layer may be lower than that of the top layer.
  • the silver halides can be obtained from regular crystals, e.g. Cubes or octahedra or tetradecahedron exist. However, tabular shaped twin crystals having an aspect ratio of 3: 1 to 30: 1 or more can also be used.
  • the crystals both the regular crystals and the tabular crystals, can have a layer structure, the halide composition of the individual layers being different.
  • the layer structures are preferably constructed as core / shell crystals, the iodide preferably being present in the core in amounts of up to 40 mol%, while the shell has an iodide content between 0-5 mol%.
  • the total iodide content of the crystals can be adjusted by the ratio of core to shell and is ⁇ 15 mol%, iodide based on the total silver of the crystal, but preferably ⁇ 10 mol% iodide.
  • the crystals can also be made up of several shells, it being possible for AgBrCl and AgBrICl to be present in the layers in addition to AgBr, AgBrI.
  • the silver halides can also be produced by converting already precipitated silver halides with another halide.
  • silver chloride with alkali or ammonium bromide can easily be converted into silver bromide, likewise silver chloride or bromide can be easily or completely converted into silver iodide.
  • concentration of the conversion halide having to be calculated according to the solubility differences, depending on the type of halide present.
  • the silver halide crystals can also be produced by producing very fine-grained emulsions and subsequent redissolving.
  • the redissolution can also be carried out by mixing two emulsions which differ in crystal size and / or the halide composition. The redissolution takes place by lowering the pBr value to values from 0.6 to 2, preferably from 0.8 to 1.2, at temperatures between 40 ° C. and 80 ° C.
  • silver halide solvents such as ammonia, thiocyanates or thioethers can be added.
  • the silver halides can be crystals which can be obtained by epitaxial growth, for example silver chloride can grow on silver bromide or silver iodide on silver bromide. Emulsions this Containing crystal forms show rapid developability (JE Makasky, Photogr. Sci. Eng. 25 (1981), No. 3, pp. 96-101).
  • the emulsions can have monodisperse crystals, i.e. at least 90% of the grains have grain sizes that are ⁇ 60%, preferably ⁇ 40% within the mean grain size.
  • the emulsions can also be polydisperse.
  • the projection area of the tabular crystals is at least 75% of the projection area of all existing crystals.
  • the thickness of the tabular crystals is between 0.4 ⁇ m and 0.1 ⁇ m. These grains are distinguished by a very rapid development (Research Disclosure (1983), No. 225 (22534)), pp. 20-58).
  • the silver halides can also have an internal image which is obtained by chemically ripening the crystals and then striking a further layer of a silver halide on the ripened crystals.
  • the (colorless and colored) color couplers used in the material according to the invention are those which couple very quickly in the color winder used under the respective development conditions (e.g. development temperature).
  • the method for measuring the clutch speed is specified in DE-OS-2 704 797.
  • the measuring methodology and the apparatus structure for determining the coupling rate constants of the couplers and DIR couplers used in the material according to the invention are described below.
  • the k value can also depend on the type and amount of solvent (oil former), as well as on the type of wetting agent and the size of the droplets. For this reason, it is desirable as a decision criterion for the usability of the coupler or DIR coupler in the sense of the present invention directly on the effective reaction rate constant (k eff ) of the couplers in their respective dispersion form. It is therefore expedient to use the couplers in the same dispersion form in which they should also be used in the color photographic material in order to determine the relative reaction rate.
  • the measuring apparatus shown in Fig. 3 consists of the cylindrical, approximately 25 cm high storage containers 1 and 2, the supply lines 3 equipped with check valves, the mixing chamber 4, the solenoid valve 5, which is closed in the idle state and opened via the pulse generator 6 the collecting vessel 7, in which a negative pressure is generated and maintained, the measuring electrode 8a, the reference electrode 8b, the digital mV meter 9 and the recorder 10.
  • the solenoid valve 5 is opened for a time t by means of the pulse generator 6.
  • the liquids contained in the latter flow via the feed lines 3 into the mixing chamber, where intensive mixing takes place.
  • the mixture then passes through the solenoid valve 5 into the collecting vessel 7.
  • Storage container 1 contains an oxidizing agent, e.g. a 10 ⁇ 3 molar aqueous solution of K3 [Fe (CN) 6].
  • Storage container 2 contains a color developer, the coupler to be examined and means for adjusting the desired pH (buffer), all in aqueous solution.
  • N1-ethyl-N1 (2-hydroxyethyl) -3-methyl-1,4-diammonium sulfate (monohydrate) Konzentration CD 4 was used (concentration: 2x10 ⁇ 3 mol / l). The concentration of the coupler to be measured was 10 ⁇ 3 mol / l.
  • Couplers that are not soluble in water can be used in the form of an emulsified from coupler, coupler solvent and hydrophilic binder, which is produced in a known manner. The pH was adjusted to 10.2 using a carbonate / bicarbonate buffer.
  • the redox potential in the mixture is measured with the measuring electrode 8a (platinum wire ⁇ 1 mm); an Ag / AgCl electrode (eg Argenthal cartridge) serves as the reference electrode 8b, which in this embodiment is located in the feed line of the reservoir 2 to the mixing chamber, but can also be attached as usual next to the platinum electrode.
  • the measured redox potential of the mixed solutions can be read with the aid of the digital mV meter 9 and the chronological course can be recorded by means of the recorder 10 (compensation recorder, oscillograph, light-point line recorder).
  • the method can also be modified in many ways. So other color developers can be used and the reaction can be run at different pH values.
  • the apparatus can be modified so that instead of the one mixing chamber 4, a system of two series-connected mixing chambers is used, the developer oxidation product being mixed in the first mixing chamber by mixing developer and ferricyanide together is generated, which is then mixed together with the coupler to be measured only in the second mixing chamber.
  • the concentration on the developer oxidation product is mainly detected by the measuring electrode, which is probably the quinone diimine of the corresponding color developer used.
  • J. Eggers “About the subsequent reactions at the Oxidation of p-amino-N-dialkylanilines "in” Messages from the Agfa research laboratories ", Volume III, page 73 (1961).
  • the couplers or DIR couplers are converted into an emulsifier with which the measurements described above are carried out in the following manner: 2 g of coupler are dissolved in 8 ml of a solvent mixture consisting of one part of dibutyl phthalate, three parts of ethyl acetate and 0.1 part of di-n-octyl sulfosuccinate (mannoxol) and emulsified in 37.5 g of 7.5% gelatin. The emulsate is then stirred for 6 min at about 1000 rpm, during which it heats up to a maximum of 60 ° C. and the ethyl acetate is then suctioned off in a water jet vacuum (200-300 mbar). Then make up to 60 g with water. The part corresponding to 1 mmol of coupler is removed from this solution and made up to 100 g with 4% gelatin. 20 ml of solution are used for each measurement.
  • the coupling rate constants designated k in the further course relate to the effective reaction rate constants k eff determined with the method described above.
  • Suitable for the material according to the invention are all those couplers whose coupling rate constant at the pH of the color developer is k ⁇ 104 [l / mol ⁇ sec].
  • the DIR couplers used in the color photographic recording material according to the invention must also have a high coupling speed (k ⁇ 104 [l / mol ⁇ sec]) so that they can compete with color and mask couplers in color coupling in the color developer. Otherwise they provide no or only insufficient DIR effects in the image-relevant color density range.
  • the same measuring method is used to measure the coupling speed as for the color and color mask couplers.
  • DIR couplers whose inhibitors have a high diffusibility are preferably used in the color photographic recording material according to the invention.
  • D ⁇ 0.4 some DIR couplers with a sufficiently high diffusibility (D ⁇ 0.4) are compiled, both those that couple sufficiently quickly in the sense of this invention (k ⁇ 104 [l / mol ⁇ sec]) without the DIR couplers to be used in the material according to the invention should be limited to these substances.
  • the difference in the coupling rate constants between the color and DIR couplers should not be more than a factor of 5, preferably not more than a factor of 2.
  • Gelatin is preferably used as a binder for the emulsions according to the invention. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion.
  • the production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). Gelatins with a high viscosity and a low content of calcium and iron ions are particularly advantageous.
  • the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58.
  • Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.)
  • Benzotriazoles can also be used as antifoggants or benzothiazolium salts can be used.
  • mercaptobenzthiazoles mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also containing a water-solubilizing group, for example a carboxyl group or sulfo group.
  • a water-solubilizing group for example a carboxyl group or sulfo group.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the present invention may contain surface active agents, viscosity increasing agents or other agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg development acceleration, high contrast, sensitization, etc.) Fluorosurfactants are particularly advantageous as casting aids.
  • the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromide or silver bromide iodide.
  • the emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
  • coupler types listed below can also be used.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; suitable examples of this are known in the literature.
  • Color couplers for producing the yellow partial color image are usually couplers with an open-chain ketomethylene grouping, in particular couplers of the type ⁇ -acylacetamids; Suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers, which are also known from the literature.
  • Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Suitable examples of this are described in large numbers in the literature.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling.
  • the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), the white couplers that react with Color developer oxidation products result in essentially colorless products.
  • the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the DIR couplers described above as well as DAR or. FAR coupler. Quick-coupling 2-equivalent couplers, which split off such escape groups in the color coupling that accelerate the development, are particularly advantageous for the material according to the invention.
  • DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-1 547 640). Because of the small amounts in which such auxiliary couplers are used, it is hardly a disadvantage if these auxiliary couplers provide a different color for the color coupling than the color couplers contained in the layer in question.
  • the cleavable residue can also be a ballast residue, so that when reacting with color developer oxidation products, coupling products are obtained which are diffusible or at least have a weak or restricted mobility, so that the granularity is reduced by the microfibre clouds being washed away (US Pat. No. 4,420,556) ).
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers.
  • oil formers so-called oil formers.
  • Appropriate Methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.
  • oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.
  • a color photographic material typically comprises at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support.
  • the order of these layers can be varied as desired. Usually blue-green, purple and yellow dyes forming couplers are in the red, green and blue sensitive Emulsion layers incorporated. However, different combinations can also be used.
  • Each of the light-sensitive layers for a spectral range can consist of a single layer or also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • the green or Red-sensitive layers can be chosen without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
  • the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sub-layer with the higher sensitivity will be arranged further away from the support than the sub-layer with lower sensitivity.
  • Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. be separated by layers of other spectral sensitization.
  • all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A 1 958 709, DE-A 2 530 645, DE-A 2 622 922).
  • layer arrangements in which more than two sub-layers are sensitive to the same spectral range e.g. a high, a medium and a low sensitive sub-layer have proven to be advantageous.
  • the middle and the low-sensitive sub-layer can be combined, while the most sensitive sub-layer for the same area can be arranged alternately above it with the most sensitive sub-layers of the other spectral ranges.
  • Intermediate layers insensitive to light can also be applied between the layers with the same color sensitivity.
  • the photographic material may further contain UV light absorbing compounds, spacers, filter dyes, formalin scavengers and others.
  • Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
  • Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A 3 533 794), 4-thiazolidone compounds (US-A 3 314 794 and 3 352 681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US-A 3 705 805 and 3 707) 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).
  • Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
  • ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
  • Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styrene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
  • binder layers in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
  • photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • binders of the material according to the invention are hardened with suitable hardeners, for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type.
  • dizine, triazine or 1,2-dihydroquinoline series hardeners are also suitable.
  • the binders of the material according to the invention are preferably hardened with instant hardeners.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • Antistatic agents for reducing the electrostatic charge can be applied to the back and / or to the surface of the materials according to the invention.
  • the materials according to the invention are processed in the usual manner according to the processes recommended for this.
  • Emulsion 1 (comparison, slow developing, highly sensitive)
  • a highly sensitive AgBrI emulsion with 11 mol% iodide was prepared by running the silver nitrate solution into a solution which contained gelatin in addition to potassium bromide and potassium iodide.
  • the temperature was 70 ° C., the pH 6.5 and the pAg at the end of the precipitation 8.7.
  • polystyrene sulfonic acid was added to the emulsion, the temperature was brought to 25 ° C. and the pH was lowered to 3.5. The emulsion flocculated and was washed until the pAg was 7.5.
  • the redispersion was carried out by raising the pH to 6.5 and heating the emulsion to 40 ° C. Gelatin was added to the emulsion until the gelatin / silver ratio was 0.7. The emulsion was then ripened to the optimum sensitivity with the addition of sulfur compounds and gold salts. The average grain diameter of the polydisperse emulsion was 0.9 ⁇ m. The electron microscopic observation showed that in addition to compact crystals, plate-shaped crystals were also present.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the emulsion was stabilized as indicated in the layer structure example 1A, mixed with the additives indicated in layer no. 4 of structure 1A (based on 100 g of AgNO3) and cast with an order of 6.0 g of AgNO3 per m2.
  • Emulsion 2 (comparison, slow developing, low sensitive)
  • a less sensitive AgBrI emulsion with 8 mol% iodide was prepared by simultaneously running a 2 molar silver nitrate solution and a 2 molar potassium bromide solution into a gelatin solution which additionally contained potassium bromide and the corresponding amount of potassium iodide.
  • the temperature was 55 ° C.
  • the pAg was kept constant at 8.3 during the precipitation. After the silver halide had been precipitated, the procedure described in Example 1 was followed.
  • Crystals with a preferably cubic shape were obtained, the mean grain diameter being 0.45 ⁇ m.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the emulsion was stabilized as indicated in layer structure 1A, mixed with the additives indicated in layer no. 3 of structure 1A (based on 100 g of AgNO3) and cast with an order of 4.0 g of AgNO3 per m2.
  • Emulsion 3 (fast developing, highly sensitive)
  • a highly sensitive silver bromide iodide emulsion containing 7 mol% iodide was prepared by mixing an aqueous gelatin solution with KBr (pBr 1.45) and 350 mg of 1,8-dihydroxy-3,6-dithiaoctane as the silver halide solvent. The temperature was brought to 70 ° C. In this solution, an aqueous AgNO3 solution and a mixture of KBr and KI, dissolved in water, were run in simultaneously, the AgNO3 content 30% of the total amount of silver and the amount of KI 24 mol%, based on the added silver nitrate amounted to.
  • the remaining 70% of the silver nitrate solution was run in simultaneously with the KBr solution, the pBr value being kept at 1.45.
  • the inflow took place with increasing flow velocity, the inflow being increased by a factor of 6.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg.
  • the emulsion was stabilized like emulsions 1 and 2, mixed with the additives specified in layer no. 13 of layer structure 2C (based on 100 g of AgNO3) and poured with an order of 6.0 g of AgNO3 per m2.
  • Emulsion 4 (fast developing, low sensitivity)
  • a less sensitive AgBrI emulsion with 5 mol% iodide was prepared by mixing an aqueous gelatin solution with the calculated amount of KI and KBr, with the pBr set to 1.65. The temperature was set at 55 ° C. and the silver nitrate solution and the equimolar potassium bromide solution were run in in 15 minutes. Cube-shaped crystals with an average diameter of 0.42 ⁇ m were obtained, 90% of the grains deviating from the average grain size by no more than ⁇ 60%.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the emulsion was stabilized like emulsions 1 and 2, mixed with the additives indicated in layer no. 3 of layer structure 1D (based on 100 g of AgNO3) and poured with an order of 4.0 g of AgNO3.
  • Emulsion 5 (comparison, highly sensitive, slowly developing)
  • a platelet-shaped emulsion containing 12 mol% of iodide was prepared by mixing a 1% by weight gelatin solution with enough KBr to achieve a pBr of 1.0.
  • a 1.2 molar AgNO3 solution and a 1.2 molar KBr solution ran at 55 ° C. in 5 minutes. in an amount equal to 2.5% of the total silver used for the emulsion preparation.
  • a mixture of 1.06 mol KBr and 0.14 mol KI was fed simultaneously with 1.2 mol AgNO3 in 52 min with increasing dosage. A total of 205 g AgNO3 were consumed.
  • the gelatin silver halide emulsion was flocculated, washed, redispersed and additional gelatin was added. Then it was ripened optimally with sulfur and gold compounds.
  • the silver bromide iodide grains contained 12 mol% iodide and preferably showed platelet-shaped crystals with an average grain diameter of 1.85 ⁇ m. The thickness was approximately 0.15 to 0.20 ⁇ m.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer no. 9 of layer structure 2A (based on 100 g of AgNO3) and cast with an order of 6.0 g of AgNO3 per m2.
  • Emulsion 6 (highly sensitive, fast developing)
  • the emulsion was flocculated, washed, redispersed and additional gelatin was added and optimally ripened with sulfur and gold salts.
  • the silver bromide iodide crystals contained 8 mol% iodide and were preferably platelet-shaped with an average grain diameter of 1.8 ⁇ m. The thickness was about 0.12 ⁇ m.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer 9 of layer structure 2D (based on 100 g of AgNO3) and cast with an order of 6.0 g of AgNO3 per m2.
  • Emulsion 7 (fast developing, low sensitivity)
  • a fine-grained, less sensitive emulsion the silver halide crystals of which consist of several layers with different halide compositions, was prepared by the double-jet process using methylimidazole as silver halide solvent at a pAg of 8.
  • a 0.5 molar AgNO3 solution and a 0.5 molar KBr solution were run into the gelatin solution simultaneously at 63 ° C left until 10% of the total silver was used up. Thereafter, in a second double inlet with a 2 molar AgNO3 solution and a further solution which contained 1.76 mol of KBr and 0.24 mol of KI, a further 60% of the silver was added for crystal formation.
  • the silver halide crystal consists of three zones, the core consisting of pure AgBr, followed by a zone which contains 12 mol% iodide and an outer zone, which in turn consists of pure AgBr.
  • the emulsion was flocculated as usual, washed and, after adding more gelatin, optimally ripened with sulfur and gold compounds.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer 3 of layer structure 2D (based on 100 g of AgNO3) and cast with an order of 2.5 g of AgNO3 per m2.
  • Emulsion 8 (fast developing, low sensitivity)
  • a fine grain, low sensitivity emulsion was prepared as in Example 7, but with an additional one AgClBr layer was installed.
  • the structure of the finished crystal had the following composition: innermost layer (34%): AgBr, 2nd layer (36%): AgBrI with 20 mol% iodide, 3rd layer (4%): AgClBr and 50 mol% chloride , outermost layer (26%); AgBrI and 5 mol% iodide.
  • the crystals were cube-shaped with an edge length of 0.5 ⁇ m.
  • the emulsion was flocculated, washed, provided with additional gelatin and optimally ripened with sulfur compounds and gold salts.
  • the silver halide concentration is equivalent to 100 g AgNO3 per kg emulsion.
  • the emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer no. 7 of layer structure 2D (based on 100 g of AgNO3) and cast with an order of 1.0 g of AgNO3 per m2.
  • UV absorber UV-1 UV absorber UV-1
  • Emulsion No. 4 in the 3rd, 6th and 9th layers Emulsion No. 3 in the 4th, 7th and 10th layers (Quantities as specified for layer structure A to C).
  • the color development, bleaching, fixing and stabilizing baths had the following composition.
  • the quantities refer to 1000 ml.
  • the layer structure 1D according to the invention is much more resistant to the deviations from the exact type conditions than the comparison structures 1A to 1C.
  • the interimage effect which improves the color quality also remains increased by the combination 1D according to the invention.
  • Example 2 Analogously to Example 1, four layer structures are compared with one another, layer structures 2A, 2B and 2C serving as a comparison and 2D representing the layer structure according to the invention.
  • the samples of the layer structures 2A to 2D were exposed and processed like those from Example 1.

Claims (9)

  1. Matériau d'enregistrement pour photographie en couleurs constitué par un support et par au moins une couche d'émulsion à l'halogénure d'argent appliquée sur le support, à laquelle est attribuée au moins un copulant chromogène à constante de vitesse de copulation à un pH de 10,2 et à 38°C ≧ 10⁴ [l/mole·sec] et au moins un copulant DIR à constante de vitesse de copulation à un pH de 10,2 et à 38°C ≧ 10⁴ [l/mole·sec], caractérisé en ce qu'on utilise une émulsion à l'halogénure d'argent qui, avec les copulants chromogènes et DIR mentionnés ci-dessus à 38°C dans un révélateur chromogène ayant la composition ci-après tripolyphosphate de sodium 2,0 g sulfite de sodium (anhydre) 2,0 g hydrogénocarbonate de sodium 8,0 g hydrogénosulfate de potassium ou de sodium 7,0 g bromure de potassium 1,8 g carbonate de potassium ou de sodium (anhydre) 30,0 g sulfate d'hydroxylamine 3,0 g sulfate de N¹-éthyl-N¹-(2-hydroxyéthyl)-3-méthyl-1,4-phénylène-diammonium (monohydraté) 2,6 g eau, pour compléter à 1000 ml
    pH = 10,2
    Figure imgb0057
     d'au moins 50 %.
  2. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que l'émulsion à l'halogénure d'argent présente une densité chromatique maximale relative d'au moins 70 %.
  3. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que l'inhibiteur séparé du copulant DIR présente une diffusibilité ≧ 0,4.
  4. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce qu'il contient des copulants des classes ci-après :
    a) des copulants chromogènes à 2 équivalents pour le jaune du type du benzoylacétanilide et/ou du type du pivaloylacétanilide
    b) des copulants chromogènes pour le magenta du type du pyrazolo-azole et/ou du type de l'acylaminopyrazolone
    c) des copulants chromogènes pour le bleu-vert du type du 2-uréidophénol et/ou du type du 5-amino-1-naphtol
    d) des copulants chromogènes pour le rouge formateurs de masque contenant un groupe O séparable, répondant à la formule générale



            Cp-O-L(₀₋₁)-Dye



    dans laquelle
    Cp représente un copulant chromogène pour le bleu-vert
    L représente un chaînon
    Dye représente un colorant à λmax entre 510-590 nm.
  5. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que, dans le cas de couches multiples à sensibilité spectrale identique, les copulants chromogènes des couches partielles à sensibilité supérieure présentent une constante de vitesse de copulation supérieure à celle des couches partielles moins sensibles.
  6. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que, dans les couches partielles du matériau d'enregistrement pour photographie en couleurs, sont également contenus des mélanges de plusieurs émulsions à développement rapide et/ou des mélanges de plusieurs copulants chromogènes à copulation rapide et/ou des mélanges de plusieurs copulants DIR à copulation rapide dont les inhibiteurs présentent une diffusibilité élevée.
  7. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, contenant au moins chaque fois une couche sensible au bleu, une couche sensible au vert et une couche sensible au rouge, caractérisé en ce qu'au moins une des couches sensibles au bleu, au vert ou au rouge présente une émulsion à l'halogénure d'argent à densité chromatique maximale relative d'au moins 50 %, des copulants chromogènes à constante de vitesse de copulation à un pH de 10,2 et à 38°C ≧ 10⁴ [l/mole·sec], des copulants DIR à constante de vitesse de copulation à un pH de 10,2 et à 38°C ≧ 10⁴ [l/mole·sec] et des inhibiteurs séparés des copulants DIR ayant une diffusibilité ≧ 0,4.
  8. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce qu'il contient des accélérateurs de développement et/ou des accélérateurs de gonflement.
  9. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que la différence dans les constantes de vitesse de copulation entre les copulants chromogènes et les copulants DIR s'élève au maximum à un facteur de 5.
EP89102221A 1988-02-19 1989-02-09 Matériau de reproduction photographique couleur Expired - Lifetime EP0329016B1 (fr)

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DE3805173 1988-02-19

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CA2022271C (fr) * 1989-07-31 1996-03-12 Soya Takagi Alliage a base de cuivre renforce par dispersion et revetement ainsi obtenu
US5399465A (en) * 1993-01-15 1995-03-21 Eastman Kodak Company Method of processing reversal elements comprising selected development inhibitors and absorber dyes
EP0608956A1 (fr) * 1993-01-29 1994-08-03 Eastman Kodak Company Elément photographique et procédé avec réponse améliorée aux variations concernant le révélateur
JP3359464B2 (ja) * 1995-02-07 2002-12-24 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料及び画像形成方法
DE69608613T2 (de) * 1995-06-27 2000-11-30 Fuji Photo Film Co Ltd Farbphotographisches Silberhalogenidmaterial und Verfahren zur Bildherstellung
DE19616497C2 (de) * 1996-04-25 2001-11-08 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial

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DE3346621A1 (de) * 1983-12-23 1985-07-04 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial und entwicklungsverfahren
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EP0329016A3 (en) 1990-08-16

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