EP0537545B1 - Produit photographique à l'halogénure d'argent - Google Patents

Produit photographique à l'halogénure d'argent Download PDF

Info

Publication number
EP0537545B1
EP0537545B1 EP92116620A EP92116620A EP0537545B1 EP 0537545 B1 EP0537545 B1 EP 0537545B1 EP 92116620 A EP92116620 A EP 92116620A EP 92116620 A EP92116620 A EP 92116620A EP 0537545 B1 EP0537545 B1 EP 0537545B1
Authority
EP
European Patent Office
Prior art keywords
silver halide
emulsion
layer
mol
oder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92116620A
Other languages
German (de)
English (en)
Other versions
EP0537545A1 (fr
Inventor
Peter Dr. Bell
Cuong Dr. Ly
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0537545A1 publication Critical patent/EP0537545A1/fr
Application granted granted Critical
Publication of EP0537545B1 publication Critical patent/EP0537545B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03517—Chloride content
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03535—Core-shell grains
    • 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
    • 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
    • Y10S430/156—Precursor compound
    • Y10S430/158—Development inhibitor releaser, DIR

Definitions

  • the invention relates to a color photographic silver halide material with at least one silver halide emulsion layer containing a color coupler, the silver halide grains of which have a layered grain structure, and which is assigned a DIR compound, the reaction of which with the oxidized color developer proceeds with a high reaction rate constant.
  • the object of the invention was to provide a color photographic silver halide material which can be developed in a short-term process and yet has excellent sharpness and color rendering.
  • the invention therefore relates to a color photographic silver halide material with at least one silver halide emulsion layer containing at least one color coupler, the silver halide grains of which contain 40 to 90 mol% of AgCl and at least two zones of different halide composition, the outer zone having a chloride content which is at least 10 mol% higher than that inner zone, and which is assigned a DIR compound whose reaction with the oxidized color developer has a reaction rate constant k> 2000 [l / mol ⁇ s].
  • a zone is said to comprise at least 5 mol% of the total silver halide, preferably at least 10 mol%.
  • the silver halide grains can also contain layers of different halide compositions which make up less than 5 mol% of the total silver halide.
  • the silver halide grains essentially contain silver bromide and optionally up to 15 mol% of silver iodide. They are preferably AgBrCl emulsions.
  • each zone comprises at least 10 mole percent silver halide, especially at least 20 mole percent.
  • the boundaries between zones of different halide compositions can be sharp or unsharp.
  • the boundary between adjacent zones is defined by the fact that at the boundary the halide content of a particular halide is equal to the mean of the halide contents of the same halide of the homogeneous regions of the adjacent zones.
  • the silver halide can be predominantly compact crystals, e.g. B. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals can also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is greater than 5: 1, e.g. B. 12: 1 to 30: 1.
  • the average grain size of the emulsions is preferably between 0.2 »m and 2.0» m, the grain size distribution can be both homo- and heterodisperse.
  • the emulsions can also contain organic silver salts, e.g. B. silver benzotriazolate or silver behenate.
  • Monodisperse emulsions are particularly preferred in which at least 70% of the spheres equal in volume to the emulsion grains have diameters that are between 0.8 times and 1.3 times the most frequent ball diameter.
  • the distribution is determined using electrolytic methods (DE-A 2 025 147).
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
  • the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the composition of the water-soluble silver salts and the halides is carried out either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
  • so-called inverse precipitation with excess silver ions is also possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Oswald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
  • Gelatin is preferably used as the binder. 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-vinylpyrolidone, 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 by reaction enough suitable layers can be produced 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). High viscosity, low swelling gelatins are particularly advantageous.
  • the gelatin can be partially or completely oxidized.
  • 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 or benzothiazolium salts can also be used as antifoggants.
  • Heterocycles containing mercapto groups e.g. B.
  • 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 silver halide emulsions are usually chemically ripened, for example by the action of Gold compounds, other precious metal compounds, reducing agents and / or divalent sulfur compounds.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active 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 acceleration of development, high contrast, sensitization etc.).
  • 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.
  • Color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer. These emulsion layers become non-diffusing monomers or polymers Color couplers assigned, which can be in the same layer or in a layer adjacent to it. Usually, cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers. At least one of these layers preferably contains the combination of emulsion and DIR compound according to the invention. Both the at least one red-sensitive and at least one green-sensitive and at least one blue-sensitive layer preferably contain the emulsion / DIR compound combination according to the invention.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; preferably 2-ureidophenol compounds and 1,5-aminonaphthol compounds.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; preferred classes of couplers are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetaninilide 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; preferred classes of couplers are pyrazoloazole and arylaminopyrazolone compounds.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. Latter 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 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears during color coupling or is replaced by the color of the image dye produced (mask coupler), for example red-mask couplers consisting of a cyan coupler and one
  • the white coupler which binds via an oxygen atom and optionally a link in the coupling point and has an absorption in the range from 510 to 590 nm, gives essentially colorless products when reacted with color developer oxidation products.
  • the 2-equivalent couplers also include the DIR couplers to be used according to the invention with a high coupling speed.
  • 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 in such a way that first of the compound in question a solution, dispersion or emulsion is prepared and then added 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. Corresponding 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 Connections eg of dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers for other couplers and other compounds are e.g. Alkyl phthalates, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.
  • 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. Couplers that form blue-green, purple and yellow dyes are usually incorporated into the red, green or blue-sensitive emulsion layers. However, different combinations can also be used.
  • Each of the light-sensitive layers can consist of a single layer or can 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 sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
  • Partial layers of the same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different 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).
  • the photographic material may further contain UV light absorbing compounds, whites, 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.
  • Suitable whiteners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.
  • 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 ethyleneimine type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneimine type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneimine 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.
  • 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.
  • solvent oil former
  • the required measuring equipment consists of two cylindrical, approximately 25 cm high storage containers, of which feed lines lead to a mixing chamber.
  • the supply lines are equipped with check valves.
  • a line leads from the mixing chamber via a solenoid valve, which is closed in the idle state and can be opened via a pulse generator, to a collecting vessel in which a negative pressure is generated and maintained.
  • a measuring electrode is arranged between the mixing chamber and the collecting vessel, a reference electrode between the mixing chamber and a storage vessel. The electrodes are connected to a digital mV meter and a recorder. The sketch of such an apparatus is described in EP-A-329 016.
  • the solenoid valve is opened for a time t by means of the pulse generator.
  • the first reservoir contains a Oxidizing agent, for example a 10 ⁇ 3 molar aqueous solution of K3 [Fe (CN) 6].
  • the second storage container contains a color developer, the coupler to be examined and means for setting the desired pH (buffer), all in aqueous solution.
  • N1-ethyl-N1 (2-hydroxyethyl) -3-methyl-1,4-diammonium sulfate (monohydrate) CD 4 was used as the color developer (concentration: 2x10 ⁇ 3 mol / l).
  • 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.
  • a pH of 10.2 was set using a carbonate / bicarbonate buffer.
  • the redox potential in the mixture is measured with the measuring electrode (platinum wire ⁇ 1 mm);
  • An Ag / AgCl electrode e.g. Argenthal cartridge
  • the measured redox potential of the mixed solutions can be read using the digital mV meter and the chronological course of the time can be recorded using the recorder (compensation recorder, oscillograph, light dot line recorder).
  • the measured redox potential is plotted in mV (ordinate) as a function of time in sec (abscissa).
  • t represents the opening time of the solenoid valve.
  • the mixing chamber and the supply and discharge lines are rinsed vigorously by opening the solenoid valve for a longer time, and the containers are then refilled to the original level.
  • the solenoid valve By briefly opening the solenoid valve the potential-time curve can then be recorded.
  • the angle ⁇ between the time axis and the tangent to the measurement curve at the beginning of the reaction is determined, once with the coupler to be measured ( ⁇ K ) and once again without a coupler ( ⁇ 0).
  • the effective reaction rate constant k eff can be determined by inserting the two ⁇ values in the above equation.
  • 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 one mixing chamber, a system of two series-connected mixing chambers is used, the developer oxidation product being produced in the first mixing chamber by mixing developer and ferricyanide together is then mixed 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.
  • the measuring electrode which is probably the quinone diimine of the corresponding color developer used.
  • Couplers or DIR couplers are converted into an emulsifier with which the measurements described above are carried out in the following manner:
  • couplers 2 g 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% by weight aqueous gelatin solution. 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.
  • the link L can also be split off by reaction with the oxidized product of a developer substance.
  • Typical examples of such links are given in the following general DIR coupler structures. wherein R38 is an aliphatic, an aromatic, a heterocyclic group or represents, l can have the values 0, 1 or 2 and p can have the values 0, 1, 2 or 3.
  • DIR couplers are suitable for the material according to the invention, the coupling rate constant of which is k 10 2 ⁇ 103, preferably ⁇ 5 ⁇ 103 [l / mol ⁇ sec] at the pH of the color developer.
  • DIR compounds whose inhibitors are highly diffusible are preferably suitable for the material according to the invention.
  • the diffusibility D f is determined for the purposes of the present invention according to the following rule:
  • Multilayer test materials A and B were made as follows:
  • test material B was also produced in the same way, but with the change compared to test material A that layer 2 is composed 0.346 g white coupler and 0.900 g gelatin.
  • test materials A and B are exposed in a dark room under room lighting with a 100 watt incandescent lamp at a distance of 1.5 m and an exposure time of 15 min.
  • Modified developers containing the development inhibitor to be tested are prepared in such a way that a 0.02 molar solution of the inhibitor in a methanol / water mixture (8: 2), which, if necessary, NaOH up to a pH of 9 contains, the developer is added and results in a 20 vol% diluted developer by adding water.
  • Test materials A and B are each developed in the developer not containing the inhibitor and processed in the further steps.
  • the resulting blue green densities are measured with a densitometer.
  • Preferred inhibitors have a D f ⁇ 0.4.
  • Inhibitors of high diffusibility to be used according to the invention are given below, the DIR compounds which can be used not being restricted to these inhibitors.
  • the color photographic silver halide materials according to the invention are processed after image-wise exposure by developing, bleaching and fixing.
  • Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N- ⁇ -hydroxyethyl-p-phenylenediamine. Further useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and
  • the pH of the color developer is in the range from 8 to 13, preferably from 9 to 12 and particularly preferably from 9.5 to 11.5.
  • the temperature is in the range from 25 to 50 ° C, preferably from 30 to 50 ° C and particularly preferably 35 to 45 ° C, in order to support the shortened development time.
  • a color developer is preferably used which contains no or less than 1.0 mg / l iodide ions. Color developers containing no or less than 50 mg / l bromide ions are particularly preferred.
  • the development time is 15 seconds to 150 seconds, preferably 20 to 120 seconds and particularly preferably 30 seconds to 90 seconds.
  • 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. Fe 3 salts and Fe 3 complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
  • Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular of ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, and alkyliminodicarboxylic acid, alkyliminodicarboxylic acid.
  • Persulphates are also suitable as bleaching agents.
  • Emulsions 2 to 4 on pages 3 and 4 are obtained analogously.
  • Emulsion 1 (Core-Shell AgCl 0.7 Br 0.3 emulsion with AgBr in the core)
  • the emulsion was flocculated; washed; redispersed with a solution of 1630 g of gelatin in 8 l of water and adjusted to pH 6.0 and pAg 8.
  • the emulsion was chemically ripened at 55 ° C. with 5 »mol sodium thiosulfate / mol Ag, 5» mol tetrachloroauric acid and 500 »mol potassium thiocyanate / mol Ag to maximum sensitivity.
  • Zone 1 made of AgBr (30 mol%)
  • Zone 2 made of AgCl (70 mol%).
  • the silver halide crystals were cubic.
  • the most common value of the diameter of the same-volume sphere was 1.6 »m, with 90% of the crystals having a diameter> 1.45» m and ⁇ 1.8 »m.
  • Emulsion 5 (Core-Shell AgCl 0.7 Br 0.3 emulsion with AgCl in the core)
  • Zone 1 made of AgCl (70 mol%)
  • Zone 2 made of AgBr (30 mol%)
  • the silver halide crystals were cubic.
  • the most common sphere diameter was 1.56 »m, with 90% of the crystals having a diameter> 1.50» m and ⁇ 1.74 »m.
  • Emulsion 6 (AgCl 0.7 Br 0.3 with an AgBr content falling from the inside to the outside)
  • a silver chloride bromide emulsion made up of 11 zones was produced by double and triple inlet processes, which contained 30 mol% AgBr in the core and 70 mol% AgCl which is not present in the center of the silver halide crystals.
  • the emulsion was flocculated, washed, redispersed and chemically ripened to maximum sensitivity.
  • the emulsion, counted from the inside out, was composed of 11 zones as follows.
  • the silver halide crystals were cube-shaped with rounded corners.
  • the most common sphere diameter was 1.84 »m, with 90% of the crystals having a diameter> 1.50» m and ⁇ 2.10 »m.
  • Emulsion 7 (AgCl 0.7 Br 0.3 with homogeneous halide distribution; comparison emulsion )
  • 1500 ml of 1.35 molar AgNO 3 solution and 1500 ml of 1 were in 9 liters of an aqueous solution containing 350 g of gelatin, 50 g of NaCl and 60 g of methionine at 55 ° C and pH 4.4 with stirring according to the double inlet method, 35 molar halide solution (70 mol% NaCl and 30 mol% KBr) were added at a rate of 55 ml / min each.
  • the emulsion was flocculated, washed, redispersed and chemically ripened to maximum sensitivity.
  • the emulsion was homodisperse and homogeneously composed of 70 mol% AgCl and 30 mol% AgBr.
  • the silver halide crystals were cubic.
  • the most common sphere diameter was 1.8 »m, with 90% of the crystals having a diameter> 1.75» m and ⁇ 1.85 »m.
  • layer structure 1B but with 2.5 g of AgNO3 the green sensitized emulsion 1 instead of 2.5 g of AgNO3 the emulsion 7.
  • Table 1 shows the values for the decrease in sensitivity ⁇ E by using DIR couplers compared to the sample without DIR couplers, the inhibition I and the edge effect K.
  • Layer structure 2D is according to the invention.
  • the interimage effect (IIE) of cyan and purple which improves the color quality is also increased by the combination (2 D) according to the invention.
  • the interimage effect is entered in Table 2 by what percentage of purple gradation and blue-green gradation is greater with green exposure or red exposure than with white exposure at the point on the color density curve where the color density obtained with white exposure is 1.0 via fog.
  • Table 2 shows the values for the edge effect and interim effect.
  • the edge effect K was determined at 1.0 macro density using fog.

Claims (7)

  1. Matériau photographique en couleurs à l'halogénure d'argent avec au moins une couche d'émulsion d'halogénure d'argent qui contient au moins un coupleur de couleurs, dont les grains d'halogénure d'argent renferment 40 à 90 % en mole d'AgCl et au moins deux zones de composition d'halogénure différente, la zone extérieure présentant un pourcentage de chlorure supérieur d'au moins 10 % en mole à celui de la zone intérieure et à laquelle est appliqué un composé DIR, dont la réaction avec le développeur couleurs oxydé a une constante de vitesse de réaction k > 2000 [l/ mole · s].
  2. Matériau photographique en couleurs à l'halogénure d'argent selon la revendication 1, dans lequel les grains d'halogénure d'argent sont des grains d'AgBrCl.
  3. Matériau photographique en couleurs à l'halogénure d'argent selon la revendication 1, dans lequel l'émulsion d'halogénure d'argent est monodispersée, au moins 70 % des grains d'émulsion présentant un diamètre de bille de même volume entre 0,8 et 1,9 fois le diamètre de bille le plus fréquent.
  4. Matériau photographique en couleurs à l'halogénure d'argent selon la revendication 1 avec au moins une couche d'émulsion d'halogénure d'argent sensible au rouge et renfermant au moins un coupleur en bleu-vert (cyan), au moins une couche d'émulsion d'halogénure d'argent sensible au vert et renfermant au moins un coupleur en magenta et au moins une couche d'émulsion d'halogénure d'argent sensible au bleu et renfermant au moins un coupleur en jaune, dans lequel au moins une couche d'émulsion d'halogénure d'argent présente une émulsion d'halogénure d'argent et un composé DIR selon la revendication 1.
  5. Matériau photographique en couleurs à l'halogénure d'argent selon la revendication 4, dans lequel au moins trois couches d'émulsion d'halogénure d'argent l'une sensible au rouge, l'une sensible au vert et l'une sensible au bleu, contiennent une émulsion d'halogénure d'argent et un coupleur DIR selon la revendication 1.
  6. Matériau photographique en couleurs à l'halogénure d'argent selon la revendication 1, caractérisé en ce que la constante de vitesse de réaction k du composé DIR est > 5 . 10³ [l/mole . s].
  7. Matériau photographique en couleurs à l'halogénure d'argent selon la revendication 1, caractérisé en ce que les inhibiteurs des composés DIR présentent une diffusibilité de ≧ 0,4.
EP92116620A 1991-10-12 1992-09-29 Produit photographique à l'halogénure d'argent Expired - Lifetime EP0537545B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4133823 1991-10-12
DE4133823A DE4133823A1 (de) 1991-10-12 1991-10-12 Fotografisches silberhalogenidmaterial

Publications (2)

Publication Number Publication Date
EP0537545A1 EP0537545A1 (fr) 1993-04-21
EP0537545B1 true EP0537545B1 (fr) 1995-01-25

Family

ID=6442554

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92116620A Expired - Lifetime EP0537545B1 (fr) 1991-10-12 1992-09-29 Produit photographique à l'halogénure d'argent

Country Status (4)

Country Link
US (1) US5270157A (fr)
EP (1) EP0537545B1 (fr)
JP (1) JPH05216187A (fr)
DE (2) DE4133823A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5547818A (en) * 1993-11-12 1996-08-20 Agfa Gevaert Ag Colour print material with variable gradation
US5512427A (en) * 1995-02-27 1996-04-30 Eastman Kodak Company Tabularly banded emulsions with high bromide central grain portions
DE19600905C2 (de) * 1996-01-12 1998-07-02 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial
US5759757A (en) * 1996-10-17 1998-06-02 Eastman Kodak Company Photographic elements containing development inhibitor releasing compounds
DE69705794T2 (de) * 1996-10-17 2002-05-23 Eastman Kodak Co Silberhalogenid-Element, das Triazol-Inhibitoren enthält
GB9827966D0 (en) * 1998-12-19 1999-02-10 Eastman Kodak Co Photographic element containing a dir coupler
US7031801B1 (en) 2003-09-19 2006-04-18 Amazon.Com, Inc. Continuous item picking in a distribution center using coordinated item picking periods
US9451674B1 (en) 2013-12-16 2016-09-20 Amazon Technologies, Inc. Inventory location illumination for designating operation path

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2704797C2 (de) * 1977-02-05 1982-05-27 Agfa-Gevaert Ag, 5090 Leverkusen Farbphotographisches Aufzeichnungsmaterial
DE3229999A1 (de) * 1982-08-12 1984-02-16 Agfa-Gevaert Ag, 5090 Leverkusen Fotografische silberhalogenidemulsion
DE3409442A1 (de) * 1984-03-15 1985-09-19 Agfa-Gevaert Ag, 5090 Leverkusen Silberchloridreiche emulsion, fotografisches aufzeichnungsmaterial und verfahren zur herstellung fotografischer aufzeichnungen
JPH0711695B2 (ja) * 1985-09-25 1995-02-08 富士写真フイルム株式会社 撮影用ハロゲン化銀カラー感光材料の処理方法
DE3819469A1 (de) * 1988-06-08 1989-12-14 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
US5155017A (en) * 1989-01-09 1992-10-13 Fuji Photo Film Co., Ltd. Silver halide photographic material

Also Published As

Publication number Publication date
JPH05216187A (ja) 1993-08-27
US5270157A (en) 1993-12-14
DE59201283D1 (de) 1995-03-09
EP0537545A1 (fr) 1993-04-21
DE4133823A1 (de) 1993-04-15

Similar Documents

Publication Publication Date Title
EP0313949B1 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0358071B1 (fr) Matériau de reproduction photographique
EP0537545B1 (fr) Produit photographique à l'halogénure d'argent
EP0464409B1 (fr) Matériau de reproduction photographique pour la couleur
EP0317886A2 (fr) Papier noir et blanc à gradation variable
EP0329016B1 (fr) Matériau de reproduction photographique couleur
EP0517053B1 (fr) Emulsion photographique à l'halogénure d'argent
EP0317885B1 (fr) Papier noir et blanc à gradation variable
EP0370226B1 (fr) Matériel photographique à l'halogénure d'argent et sa méthode de traitement
EP0627656B1 (fr) Matériau d'enregistrement photographique
EP0607801A1 (fr) Matériau photographique couleur d'enregistrement
EP0345553B1 (fr) Matériau de reproduction photographique
EP0413204A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0447656A1 (fr) Matériau photographique couleur à l'halogénure d'argent et son développement
EP0377181A2 (fr) Matériau photographique couleur
EP0377889B1 (fr) Matériel d'enregistrement à l'halogénure d'argent
EP0607800A1 (fr) Matériau photographique couleur d'enregistrement
EP0345514A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0363820A2 (fr) Matériau photographique couleur à l'halogénure d'argent
EP0315833A2 (fr) Matériau photographique couleur
EP0554756B1 (fr) Produit pour la reproduction photographique en couleur
EP0546416A1 (fr) Matériau d'enregistrement pour la photographie en couleurs
DE3744004A1 (de) Farbfotografisches aufzeichnungsmaterial und verfahren zur herstellung einer fotografischen silberhalogenidemulsion
EP0401610B1 (fr) Produit photographique couleur à l'halogénure d'argent
EP0312837A2 (fr) Procédé de traitement photographique sans lavage à l'eau et bain de stabilisation utilisé pour ce procédé

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19930714

17Q First examination report despatched

Effective date: 19940628

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950201

REF Corresponds to:

Ref document number: 59201283

Country of ref document: DE

Date of ref document: 19950309

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970811

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970910

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970922

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970924

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970930

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980930

BERE Be: lapsed

Owner name: AGFA-GEVAERT A.G.

Effective date: 19980930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990401

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990531

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050929