EP0517053A1 - Photographic silver halide emulsion - Google Patents

Photographic silver halide emulsion Download PDF

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Publication number
EP0517053A1
EP0517053A1 EP92108735A EP92108735A EP0517053A1 EP 0517053 A1 EP0517053 A1 EP 0517053A1 EP 92108735 A EP92108735 A EP 92108735A EP 92108735 A EP92108735 A EP 92108735A EP 0517053 A1 EP0517053 A1 EP 0517053A1
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EP
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Prior art keywords
silver halide
emulsion
mol
halide emulsion
photographic
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EP92108735A
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German (de)
French (fr)
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EP0517053B1 (en
Inventor
Walter Dr. Pätzold
Bruno Dr. Mücke
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • the invention relates to a photographic silver halide emulsion which is distinguished by a high maximum density, steep gradation, great sensitivity and rapid developability.
  • a flat threshold gradation can occur with these emulsions, which can lead to a flattening of the gradation and a rise in fog. Furthermore, due to the necessary strong maturation, a further increase in fog is observed, especially after storage at normal or elevated temperature.
  • the object of the invention was to avoid the disadvantages described, that is to say to produce a rapidly developing and highly sensitive silver halide emulsion which is distinguished by a steep gradation with a slight increase in fog of the material during storage.
  • Another goal was to improve threshold gradation and decrease sensitivity to subliminal pre-exposure, e.g. Darkroom light.
  • This object was achieved in that a diindolyl disulfide was added to the silver halide emulsion before the chemical ripening began.
  • the silver halide emulsion according to the invention is preferably doped with 10- 9 to 10- 4 mol / mol Ag Rh 3 + and / or Ir 4+ ions.
  • the emulsion is preferably ripened with gold and sulfur compounds, in particular in a concentration of 2 ⁇ 10 -6 to 2 ⁇ 10 -4 mol of gold compound / mol of Ag and 10- 6 to 10- 4 mol of sulfur compound / mol of Ag.
  • AgCI, AgBr, AgBrCI, AgBrl and AgBrCII come into consideration as silver halides.
  • the silver halide emulsion according to the invention preferably has a composition of AgCl 0.15 Br 0.85 to AgCl 0.999 Br 0.001 .
  • Particularly clear effects are achieved with so-called chloride emulsions, ie silver chloride bromide emulsions with chloride proportions above 80, preferably above 95 mol%.
  • the silver halide emulsion according to the invention can be used for photographic materials, particularly color negative paper and black and white negative paper.
  • Another object of the invention is therefore a photographic material with a support and at least one light-sensitive silver halide emulsion layer, characterized in that the silver halide emulsion of the silver halide emulsion layer contains a compound of formula (I) in an amount of 10- 7 to 10- 3 mol / mol Ag.
  • the photographic material of the invention can be color photographic material, e.g. a color negative film, a color negative paper, a color reversal film or a color reversal paper or a black and white material, e.g. a black and white film or black and white paper.
  • color photographic material e.g. a color negative film, a color negative paper, a color reversal film or a color reversal paper or a black and white material, e.g. a black and white film or black and white paper.
  • Suitable compounds for doping the silver halide emulsion according to the invention are, for example, Na 3 RhCl 6 and Na 2 1rC1 6 .
  • Other suitable compounds are in European Patent 336 425, 336 426 and 336 427.
  • Suitable gold ripening agents are, for example, H (AuCl4) + KSCN, Na 3 [ A U (S 2 0 3 ) 2] * 2H 2 0 and gold rhodanine. Further gold ripening agents are known from German patents 854 883 and 848 910.
  • Suitable compounds for sulfur ripening are e.g. Thiosulfates and thioureas such as N, N-dimethylthiourea and N-allylthiourea as well as thioacetamide.
  • the diindolyl disulfides according to the invention and their preparation are described in Chem. Pharm. Bull. 21 (1973), 2739.
  • the diindolyl disulfides can be added during the preparation of the emulsion.
  • the compounds according to the invention are added at any time after the end of crystal formation and before the end of chemical ripening. In a particularly preferred embodiment, the addition takes place directly before the start of chemical ripening.
  • the silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably less than 8: 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 in which the ratio of diameter to thickness is greater than 8: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
  • the average grain size of the emulsion is preferably between 0.2 .mu.m and 2.0 .mu.m, the grain size distribution can be both homo- and heterodisperse.
  • the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared by 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, e.g. 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 e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are combined 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 Ostwald 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, TI, Bi, Fe can 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-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, the Examples of these have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.
  • 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 gelatin can be oxidized.
  • 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 soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchanger.
  • 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. by 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.
  • Mercaptobenzthiazoles mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptopyrimidines, these mercaptoazoles also being a water-solubilizing group, e.g. may contain a carboxyl group or sulfo group.
  • Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.
  • 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 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.
  • Suitable supports for the production of color photographic materials are e.g. Films and foils of semisynthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or a-olefin polymer layer (e.g. polyethylene).
  • These supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
  • Color photographic materials usually contain at least one red sensitive, green sensitive and blue sensitive emulsion layer each. These 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. 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.
  • Color couplers for producing the blue-green partial color image are generally couplers of the phenol or a-naphthol type; suitable examples of this are known in the literature.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain catomethylene group, in particular couplers of the a-acylacetamide type; Suitable examples are a-benzoylacetanilide couplers and a-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 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 when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield 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 effectiveness unfolds, e.g. as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
  • DIR, DAR or FAR couplers mainly the effectiveness of the residue released during the coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR and / or FAR couplers are also important suitable, which give essentially colorless products on coupling (DE-A-1 547 640).
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (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 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 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.
  • 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 the support.
  • the order of these layers can be varied as desired. Couplers which 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).
  • There are red-sensitive Silverha logenide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, 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 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).
  • the photographic material may further contain compounds absorbing UV light, whiteners, spacers, filter dyes, formalin scavengers and others.
  • 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-4,015,229) or benzoxazole compounds (US-A-3,700,455).
  • Ultraviolet absorbing couplers such as a-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 white toners 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 17643, 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 17643, 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. Hardeners of the diazine, triazine or 1,2-dihydroquinoline series 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 caused by the crosslinking reaction and the swelling of the layer structure occurs .
  • 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 which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter also with free amino groups of the gelatin react to form peptide bonds and crosslink the gelatin.
  • Suitable examples of instant hardeners are e.g. in European Patent 313,949.
  • the materials according to the invention are processed in the usual manner according to the processes recommended for this.
  • Solutions 2 and 3 are simultaneously added to solution 1 at 50 ° C. over a period of 120 minutes at a pAg of 7.7 with vigorous stirring.
  • a silver chloride emulsion with an average particle diameter of 0.8 ⁇ m is obtained.
  • the gelatin / AgN0 3 weight ratio is 0.18.
  • the emulsion is flocked in a known manner, washed and redispersed with enough gelatin that the gelatin / AgN0 3 weight ratio is 1.0.
  • the emulsion contains 1 mol of silver halide per kg.
  • the mixture is then optimally ripened at a pH of 4.5 with 3.5 ⁇ mol gold chloride / mol Ag and 1.5 ⁇ mol Na 2 S 2 0 3 / MolAg.
  • the emulsion (silver halide composition: AgCl 0.99 Br 0.01 ) is stabilized and sensitized to the blue spectral range.
  • the emulsion is prepared and processed as described in Example 1, but with the difference that during chemical ripening, 4.5 mg of diphenylindolyl disulfide are added as a 0.1% by weight acetone solution before the thiosulfate is added.
  • the emulsion is prepared and processed as described in Example 1, but with the difference that 225 mg of diphenylindolyl disulfide are added during chemical ripening before the addition of thiosulfate.
  • Solutions 2 and 3 are simultaneously added to solution 1 at 55 ° C. in the course of 60 minutes at a pAg of 7.8 with vigorous stirring.
  • the emulsion is flocculated in a known manner, washed and redispersed with the addition of gelatin, phenol (as a preservative) and water.
  • the emulsion contains 0.9 mol of silver halide per kg.
  • the mixture is then ripened at 52 ° C. for 120 minutes with the addition of 10 ⁇ mol HAuC1 4 / mol Ag and 20 ⁇ mol Na 2 S 2 0 3 / mol Ag.
  • the emulsion (silver halide composition: AgCl o , 5 Br o , 5 ) is poured onto a paper support coated on both sides with polyethylene with the addition of sensitizers, stabilizers, plasticizer latex, optical brighteners, developer substances and hardening agents.
  • the material is exposed imagewise and processed according to the AGFA 100 recipe.
  • the emulsion is prepared and processed as described in Example 4, but with the difference that in chemical ripening, 160 mg of diphenylindolyl disulfide before the addition of the ripening substances be added.
  • the emulsion is prepared and processed as described in Example 4. However, the sensitometric data are only measured after a two-day storage at 60 ° C.
  • the emulsion is prepared and processed as described in Example 5. However, the sensitometric data are only measured after a two-day storage at 60 ° C.
  • the emulsion is produced and processed as described in Example 4, but after image-wise exposure, an additional diffuse exposure was carried out using amber filters (corresponds to the draft standard ISO / DIS 8374).
  • the emulsion is produced and processed as described in Example 5, but after image-wise exposure, an additional diffuse exposure was carried out using amber filters (corresponds to the draft standard ISO / DIS 8374).

Abstract

By means of adding a diindolyl disulphide during the preparation of the emulsion, a rapidly developing and highly sensitive silver halide emulsion is obtained which is distinguished by a steep gradation, a small rise in fog during storage, an improved threshold gradation and low sensitivity to below-threshold pre-exposure.

Description

Die Erfindung betrifft eine fotografische Silberhalogenidemulsion, die sich durch hohe Maximaldichte, steile Gradation, große Empfindlichkeit und schnelle Entwickelbarkeit auszeichnet.The invention relates to a photographic silver halide emulsion which is distinguished by a high maximum density, steep gradation, great sensitivity and rapid developability.

Es ist bekannt, daß eine hohe Maximaldichte sowie eine schnelle Entwickelbarkeit eines fotografischen Materials durch die Verwendung einer feinkörnigen Silberhalogenidemulsion erreicht werden kann.It is known that a high maximum density and rapid developability of a photographic material can be achieved by using a fine-grain silver halide emulsion.

Durch Dotierung mit Rh3⊕- und/oder Ir4⊕-lonen erhalt man ein Material mit steiler Gradation (DE-OS 2 226 877).Doping with Rh 3⊕ - and / or Ir 4⊕ ions gives a material with a steep gradation (DE-OS 2 226 877).

Um Silberhalogenidemulsionen der vorstehend genannten Art mit großer Empfindlichkeit herzustellen, ist es erforderlich, die chemische Reifung mit einer Kombination aus Gold- und Schwefelverbindungen durchzuführen (Ullmanns Encyklopädie der technischen Chemie; 4. Aufl., Bd. 18, S. 424).In order to prepare silver halide emulsions of the above-mentioned type with great sensitivity, it is necessary to carry out chemical ripening with a combination of gold and sulfur compounds (Ullmanns Encyklopadie der Technische Chemie; 4th ed., Vol. 18, p. 424).

Bei diesen Emulsionen kann als unerwünschter Nebeneffekt eine flache Schwellengradation auftreten, die zu einer Gradationsverflachung und einem Schleieranstieg führen kann. Weiterhin wird durch die notwendige starke Ausreifung ein weiterer Schleieranstieg, vor allem nach Lagerung bei normaler oder erhöhter Temperatur, beobachtet.As an undesirable side effect, a flat threshold gradation can occur with these emulsions, which can lead to a flattening of the gradation and a rise in fog. Furthermore, due to the necessary strong maturation, a further increase in fog is observed, especially after storage at normal or elevated temperature.

Aufgabe der Erfindung war es, die beschriebenen Nachteile zu vermeiden, also eine schnell entwickelnde und hochempfindliche Silberhalogenidemulsion herzustellen, die sich durch eine steile Gradation bei gleichzeitigem geringen Schleieranstieg des Materials während der Lagerung auszeichnet. Ein weiteres Ziel war es, eine Verbesserung der Schwellengradation und eine Erniedrigung der Empfindlichkeit gegenüber unterschwelliger Vorbelichtung, z.B. Dunkelkammerlicht, zu erreichen.The object of the invention was to avoid the disadvantages described, that is to say to produce a rapidly developing and highly sensitive silver halide emulsion which is distinguished by a steep gradation with a slight increase in fog of the material during storage. Another goal was to improve threshold gradation and decrease sensitivity to subliminal pre-exposure, e.g. Darkroom light.

Diese Aufgabe wurde dadurch gelöst, daß man vor dem Beginn der chemischen Reifung der Silberhalogenidemulsion ein Diindolyl-disulfid zusetzt.This object was achieved in that a diindolyl disulfide was added to the silver halide emulsion before the chemical ripening began.

Gegenstand der Erfindung ist somit eine fotografische Silberhalogenidemulsion, dadurch gekennzeichnet, daß die Emulsion 10-7 bis 10-3 Mol/Mol Silber einer Verbindung der Formel (I)

Figure imgb0001

worin

  • R1 H oder Alkyl,
  • R2 Alkyl, Benzyl, Phenyl oder substituiertes Phenyl,
  • R3, R4 H, Alkyl, Alkoxy, Halogen oder Nitro bedeuten,
  • enthält.
The invention is thus a silver halide photographic emulsion, characterized in that the emulsion 10- 7 to 10- 3 mol / mol of silver of a compound of formula (I)
Figure imgb0001
wherein
  • R 1 is H or alkyl,
  • R 2 is alkyl, benzyl, phenyl or substituted phenyl,
  • R 3 , R 4 are H, alkyl, alkoxy, halogen or nitro,
  • contains.

Die erfindungsgemäße Silberhalogenidemulsion wird vorzugsweise mit 10-9 bis 10-4 Mol/Mol Ag Rh3+- und/oder Ir4+-lonen dotiert.The silver halide emulsion according to the invention is preferably doped with 10- 9 to 10- 4 mol / mol Ag Rh 3 + and / or Ir 4+ ions.

Die Emulsion wird bevorzugt mit Gold- und Schwefelverbindungen gereift, insbesondere in einer Konzentration von 2·10-6 bis 2·10-4 Mol Goldverbindung/Mol Ag und 10-6 bis 10-4 Mol Schwefelverbindung/Mol Ag.The emulsion is preferably ripened with gold and sulfur compounds, in particular in a concentration of 2 × 10 -6 to 2 × 10 -4 mol of gold compound / mol of Ag and 10- 6 to 10- 4 mol of sulfur compound / mol of Ag.

Als Silberhalogenide kommen AgCI, AgBr, AgBrCI, AgBrl und AgBrCII in Betracht.AgCI, AgBr, AgBrCI, AgBrl and AgBrCII come into consideration as silver halides.

Die erfindungsgemäß Silberhalogenidemulsion hat bevorzugt eine Zusammensetzung von AgCl0.15Br0.85 bis AgCl0.999Br0.001. Besonders deutliche Effekte werden bei sogenannten Chloridemulsionen erzielt, d.h. Silberchloridbromidemulsionen mit Chloridanteilen über 80, vorzugsweise über 95 Mol-%.The silver halide emulsion according to the invention preferably has a composition of AgCl 0.15 Br 0.85 to AgCl 0.999 Br 0.001 . Particularly clear effects are achieved with so-called chloride emulsions, ie silver chloride bromide emulsions with chloride proportions above 80, preferably above 95 mol%.

Die der Erfindung entsprechende Silberhalogenidemulsion kann für fotografische Materialien, insbesondere für Colornegativpapier und Schwarz-Weiß-Negativpapierverwendet werden.The silver halide emulsion according to the invention can be used for photographic materials, particularly color negative paper and black and white negative paper.

Ein weiterer Gegenstand der Erfindung ist daher ein fotografisches Material mit einem Träger und wenigstens einer lichtempfindlichen Silberhalogenidemulsionsschicht, dadurch gekennzeichnet, daß die Silberhalogenidemulsion der Silberhalogenidemulsionsschicht eine Verbindung der Formel (I) in einer Menge 10-7 bis 10-3 Mol/Mol Ag enthält.Another object of the invention is therefore a photographic material with a support and at least one light-sensitive silver halide emulsion layer, characterized in that the silver halide emulsion of the silver halide emulsion layer contains a compound of formula (I) in an amount of 10- 7 to 10- 3 mol / mol Ag.

Das erfindungsgemäße fotografische Material kann farbfotografisches Material, z.B. ein Colornegativfilm, ein Colornegativpapier, ein Colorumkehrfilm oder ein Colorumkehrpapier oder ein Schwarz-Weiß-Material sein, z.B. ein Schwarz- Weiß-Film oder ein Schwarz-Weiß-Papier.The photographic material of the invention can be color photographic material, e.g. a color negative film, a color negative paper, a color reversal film or a color reversal paper or a black and white material, e.g. a black and white film or black and white paper.

Geeignete Verbindungen zur Dotierung der erfindungsgemäßen Silberhalogenidemulsion sind z.B. Na3RhCl6 und Na21rC16. Weitere geeignete Verbindungen sind in den Europäischen Patentschriften 336 425, 336 426 und 336 427 beschrieben.Suitable compounds for doping the silver halide emulsion according to the invention are, for example, Na 3 RhCl 6 and Na 2 1rC1 6 . Other suitable compounds are in European Patent 336 425, 336 426 and 336 427.

Geeignete Goldreifmittel sind z.B. H(AuCI4) + KSCN, Na3[AU(S203)2] *2H20 und Goldrhodanin. Weitere Goldreifmittel sind aus den Deutschen Patentschriften 854 883 und 848 910 bekannt.Suitable gold ripening agents are, for example, H (AuCl4) + KSCN, Na 3 [ A U (S 2 0 3 ) 2] * 2H 2 0 and gold rhodanine. Further gold ripening agents are known from German patents 854 883 and 848 910.

Geeignete Verbindungen für die Schwefelreifung sind z.B. Thiosulfate und Thioharnstoffe wie N,N-Dimethylthioharnstoff und N-Allylthioharnstoff sowie Thioacetamid.Suitable compounds for sulfur ripening are e.g. Thiosulfates and thioureas such as N, N-dimethylthiourea and N-allylthiourea as well as thioacetamide.

Die erfindungsgemäßen Diindolyl-disulfide und deren Herstellung sind in Chem. Pharm. Bull. 21 (1973), 2739 beschrieben. Die Diindolyl-disulfide können während der Emulsionsherstellung zugesetzt werden. In einer bevorzugten Ausführungsform werden die erfindungsgemäßen Verbindungen zu einem beliebigen Zeitpunkt nach dem Ende der Kristallerzeugung und vor dem Ende der chemischen Reifung zugegeben. In einer besonders bevorzugten Ausführungsform erfolgt die Zugabe direkt vor dem Beginn der chemischen Reifung.The diindolyl disulfides according to the invention and their preparation are described in Chem. Pharm. Bull. 21 (1973), 2739. The diindolyl disulfides can be added during the preparation of the emulsion. In a preferred embodiment, the compounds according to the invention are added at any time after the end of crystal formation and before the end of chemical ripening. In a particularly preferred embodiment, the addition takes place directly before the start of chemical ripening.

Bei dem Silberhalogenid kann es sich um überwiegend kompakte Kristalle handeln, die z.B. regulär kubisch oder oktaedrisch sind oder Übergangsformen aufweisen können. Vorzugsweise können aber auch plättchenförmige Kristalle vorliegen, deren durchschnittliches Verhältnis von Durchmesser zu Dicke bevorzugt kleiner als 8:1 ist, wobei der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einem Kreisinhalt entsprechend der projizierten Fläche des Korns. Die Schichten können aber auch tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke größer als 8:1 ist.The silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably less than 8: 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. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.

Die Silberhalogenidkörner können auch einen mehrfach geschichteten Kornaufbau aufweisen, im einfachsten Fall mit einem inneren und einem äußeren Kornbereich (core/shell), wobei die Halogenidzusammensetzung und/oder sonstige Modifizierungen, wie z.B. Dotierungen der einzelnen Kornbereiche unterschiedlich sind. Die mittlere Korngröße der Emulsion liegt vorzugsweise zwischen 0,2 um und 2,0 um, die Korngrößenverteilung kann sowohl homo- als auch heterodispers sein. Die Emulsionen können außer dem Silberhalogenid auch organische Silbersalze enthalten, z.B. Silberbenztriazolat oder Silberbehenat.The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different. The average grain size of the emulsion is preferably between 0.2 .mu.m and 2.0 .mu.m, the grain size distribution can be both homo- and heterodisperse. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.

Es können zwei oder mehrere Arten von Silberhalogenidemulsionen, die getrennt hergestellt werden, als Mischung verwendet werden.Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.

Die fotografischen Emulsionen können nach verschiedenen Methoden (z.B. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press, London (1966) aus löslichen Silbersalzen und löslichen Halogeniden hergestellt werden.The photographic emulsions can be prepared by 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.

Die Fällung des Silberhalogenids erfolgt bevorzugt in Gegenwart des Bindemittels, z.B. der Gelatine und kann im sauren, neutralen oder alkalischen pH-Bereich durchgeführt werden, wobei vorzugsweise Silberhalogenidkomplexbildner zusätzlich verwendet werden. Zu letzteren gehören z.B. Ammoniak, Thioether, Imidazol, Ammoniumthiocyanat oder überschüssiges Halogenid. Die Zusammenführung der wasserlöslichen Silbersalze und der Halogenide erfolgt wahlweise nacheinander nach dem single-jet- oder gleichzeitig nach dem double-jet-Verfahren oder nach beliebiger Kombination beider Verfahren. Bevorzugt wird die Dosierung mit steigenden Zuflußraten, wobei die "kritische" Zufuhrgeschwindigkeit, bei der gerade noch keine Neukeime entstehen, nicht überschritten werden sollte. Der pAg-Bereich kann während der Fällung in weiten Grenzen variieren, vorzugsweise wird das sogenannte pAg-gesteuerte Verfahren benutzt, bei dem ein bestimmter pAg-Wert konstant gehalten oder ein definiertes pAg-Profil während der Fällung durchfahren wird. Neben der bevorzugten Fällung bei Halogenidüberschuß ist aber auch die sogenannte inverse Fällung bei Silberionenüberschuß möglich. Außer durch Fällung können die Silberhalogenidkristalle auch durch physikalische Reifung (Ostwaldreifung), in Gegenwart von überschüssigem Halogenid und/oder Silberhalogenidkomplexierungsmittelwachsen. Das Wachstum der Emulsionskörner kann sogar überwiegend durch Ostwaldreifung erfolgen, wobei vorzugsweise eine feinkörnige, sogenannte Lippmann-Emulsion, mit einer schwerer löslichen Emulsion gemischt und auf letzterer umgelöst wird.The silver halide is preferably precipitated in the presence of the binder, e.g. 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 e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined 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. In addition to the preferred precipitation with excess halide, so-called inverse precipitation with excess silver ions is also possible. In addition to precipitation, 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 Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.

Während der Fällung und/oder der physikalischen Reifung der Silberhalogenidkörner können auch Salze oder Komplexe von Metallen, wie Cd, Zn, Pb, TI, Bi, Fe vorhanden sein.Salts or complexes of metals such as Cd, Zn, Pb, TI, Bi, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.

Ferner kann die Fällung auch in Gegenwart von Sensibilisierungsfarbstoffen erfolgen. Komplexierungsmittel und/oder Farbstoffe lassen sich zu jedem beliebigen Zeitpunkt unwirksam machen, z.B. durch Änderung des pH-Wertes oder durch eine oxidative Behandlung.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.

Als Bindemittel wird vorzugsweise Gelatine verwendet. Diese kann jedoch ganz oder teilweise durch andere synthetische, halbsynthetische oder auch natürlich vorkommende Polymere ersetzt werden. Synthetische Gelatineersatzstoffe sind beispielsweise Polyvinylalkohol, Poly-N-vinylpyrrolidon, Polyacrylamide, Polyacrylsäure und deren Derivate, insbesondere deren Mischpolymerisate. Natürlich vorkommende Gelatineersatzstoffe sind beispielsweise andere Proteine wie Albumin oder Casein, Cellulose, Zucker, Stärke oder Alginate. Halbsynthetische Gelatineersatzstoffe sind in der Regel modifizierte Naturprodukte. Cellulosederivate wie Hydroxyalkylcellulose, Carboxymethylcellulose und Phthalylcellulose sowie Gelatinederivate, die durch Umsetzung mit Alkylierungs- oder Acylierungsmitteln oder durch Aufpfropfung von polymerisierbaren Monomeren erhalten worden sind, sind Beispiele hierfür.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-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, the Examples of these have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.

Die Bindemittel sollen über eine ausreichende Menge an funktionellen Gruppen verfügen, so daß durch Umsetzung mit geeigneten Härtungsmitteln genügend widerstandsfähige Schichten erzeugt werden können. Solche funktionellen Gruppen sind insbesondere Aminogruppen, aber auch Carboxylgruppen, Hydroxylgruppen und aktive Methylengruppen.The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

Die vorzugsweise verwendete Gelatine kann durch sauren oder alkalischen Aufschluß erhalten sein. Die Gelatine kann oxidiert sein. Die Herstellung solcher Gelatinen wird beispielsweise in The Science and Technology of Gelatine, herausgegeben von A.G. Ward und A. Courts, Academic Press 1977, Seite 295 ff beschrieben. Die jeweils eingesetzte Gelatine soll einen möglichst geringen Gehalt an fotografisch aktiven Verunreinigungen enthalten (Inertgelatine). Gelatinen mit hoher Viskosität und niedriger Quellung sind besonders vorteilhaft.The gelatin which is preferably used can be obtained by acidic or alkaline digestion. The gelatin can be oxidized. 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.

Nach abgeschlossener Kristallbildung oder auch schon zu einem früheren Zeitpunkt werden die löslichen Salze aus der Emulsion entfernt, z.B. durch Nudeln und Waschen, durch Flocken und Waschen, durch Ultrafiltration oder durch lonenaustauscher.After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchanger.

Die fotografischen Emulsionen können Verbindungen zur Verhinderung der Schieierbildung oder zur Stabilisierung der fotografischen Funktion während der Produktion, der Lagerung oder der fotografischen Verarbeitung enthalten.The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.

Besonders geeignet sind Azaindene, vorzugsweise Tetra- und Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind z.B. von Birr, Z. Wiss. Phot. 47 (1952), S. 2-58 beschrieben worden. Weiter können als Antischleiermittel Salze von Metallen wie Quecksilber oder Cadmium, aromatische Sulfon- oder Sulfinsäuren wie Benzolsulfinsäure, oder stickstoffhaltige Heterocyclen wie Nitrobenzimidazol, Nitroindazol, (subst.) Benztriazole oder Benzthiazoliumsalze eingesetzt werden. Besonders geeignet sind Mercaptogruppen enthaltende Heterocyclen, z.B. Mercaptobenzthiazole, Mercaptobenzimidazole, Mercaptotetrazole, Mercaptothiazole, Mercaptopyrimidine, wobei diese Mercaptoazole auch eine wasserlöslichmachende Gruppe, z.B. eine Carboxylgruppe oder Sulfogruppe, enthalten können. Weitere geeignete Verbindungen sind in Research Disclosure Nr. 17643 (1978), Abschnitt VI, veröffentlicht.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. by 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. Mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptopyrimidines, these mercaptoazoles also being a water-solubilizing group, e.g. may contain a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.

Die Stabilisatoren können den Silberhalogenidemulsionen vor, während oder nach deren Reifung zugesetzt werden. Selbstverständlich kann man die Verbindungen auch anderen fotografischen Schichten, die einer Halogensilberschicht zugeordnet sind, zusetzen.The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Es können auch Mischungen aus zwei oder mehreren der genannten Verbindungen eingesetzt werden.Mixtures of two or more of the compounds mentioned can also be used.

Die fotografischen Emulsionsschichten oder andere hydrophile Kolloidschichten des erfindungsgemäß hergestellten lichtempfindlichen Materials können oberflächenaktive Mittel für verschiedene Zwecke enthalten, wie Überzugshilfen, zur Verhinderung der elektrischen Aufladung, zur Verbesserung der Gleiteigenschaften, zum Emulgieren der Dispersion, zur Verhinderung der Adhäsion und zur Verbesserung der fotografischen Charakteristika (z.B. Entwicklungsbeschleunigung, hoher Kontrast, Sensibilisierung usw.).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.).

Die fotografischen Emulsionen können unter Verwendung von Methinfarbstoffen oder anderen Farbstoffen spektral sensibilisiert werden. Besonders geeignete Farbstoffe sind Cyaninfarbstoffe, Merocyaninfarbstoffe und komplexe Merocyaninfarbstoffe.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.

Auf Sensibilisatoren kann verzichtet werden, wenn für einen bestimmten Spektralbereich die Eigenempfindlichkeit des Silberhalogenids ausreichend ist, beispielsweise die Blauempfindlichkeit von Silberbromid.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.

Geeignete Träger zur Herstellung farbfotografischer Materialien sind z.B. Filme und Folien von halbsynthetischen und synthetischen Polymeren, wie Cellulosenitrat, Celluloseacetat, Cellulosebutyrat, Polystyrol, Polyvinylchlorid, Polyethylenterephthalat und Polycarbonat und mit einer Barytschicht oder a-Olefinpolymer- schicht(z.B. Polyethylen) laminiertes Papier. Diese Träger können mit Farbstoffen und Pigmenten, beispielsweise Titandioxid, gefärbt sein. Sie können auch zum Zwecke der Abschirmung von Licht schwarz gefärbt sein. Die Oberfläche des Trägers wird im allgemeinen einer Behandlung unterzogen, um die Adhäsion der fotografischen Emulsionsschicht zu verbessern, beispielsweise einer Corona-Entladung mit nachfolgendem Antrag einer Substratschicht.Suitable supports for the production of color photographic materials are e.g. Films and foils of semisynthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or a-olefin polymer layer (e.g. polyethylene). These supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.

Farbfotografische Materialien enthalten üblicherweise mindestens je eine rotempfindliche, grünemfindliche und blauempfindliche Emulsionsschicht. Diesen Emulsionsschichten werden nicht diffundierende monomere oder polymere Farbkuppler zugeordnet, die sich in der gleichen Schicht oder in einer dazu benachbarten Schicht befinden können. Gewöhnlich werden den rotempfindlichen Schichten Blaugrünkuppler, den grünempfindlichen Schichten Purpurkuppler und den blauempfindlichen Schichten Gelbkuppler zugeordnet.Color photographic materials usually contain at least one red sensitive, green sensitive and blue sensitive emulsion layer each. These 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. 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.

Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes sind in der Regel Kuppler vom Phenol-oder a-Naphtholtyp; geeignete Beispiele hierfür sind in der Literatur bekannt.Color couplers for producing the blue-green partial color image are generally couplers of the phenol or a-naphthol type; suitable examples of this are known in the literature.

Farbkuppler zur Erzeugung des gelben Teilfarbenbildes sind in der Regel Kuppler mit einer offenkettigen Katomethylengruppierung, insbesondere Kuppler vom Typ des a-Acylacetamids; geeignete Beispiele hierfür sind a-Benzoylacetanilidkuppler und a-Pivaloylacetanilidkuppler, die ebenfalls aus der Literatur bekannt sind.Color couplers for producing the yellow partial color image are generally couplers with an open-chain catomethylene group, in particular couplers of the a-acylacetamide type; Suitable examples are a-benzoylacetanilide couplers and a-pivaloylacetanilide couplers, which are also known from the literature.

Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes sind in der Regel Kuppler vom Typ des 5-Pyrazolons, des Indazolons oder des Pyrazoloazols; geeignete Beispiele hierfür sind in der Literatur in großer Zahl beschrieben.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.

Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind solche zu rechnen, die farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), und die Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR- bzw. FAR-Kuppler.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 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 when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield 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 effectiveness unfolds, e.g. as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.

Da bei den DIR-, DAR- bzw. FAR-Kupplern hauptsächlich die Wirksamkeit des bei der Kupplung freigesetzten Restes erwünscht ist und es weniger auf die farbbildenden Eigenschaften dieser Kuppler ankommt, sind auch solche DIR-, DAR- bzw. bzw. FAR-Kuppler geeignet, die bei der Kupplung im wesentlichen farblose Produkte ergeben (DE-A-1 547 640).Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during the coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR and / or FAR couplers are also important suitable, which give essentially colorless products on coupling (DE-A-1 547 640).

Der abspaltbare Rest kann auch ein Ballastrest sein, so daß bei der Reaktion mit Farbentwickleroxidationsprodukten Kupplungsprodukte erhalten werden, die diffusionsfähig sind oder zumindest eine schwache bzw. eingeschränkte Beweglichkeit aufweisen (US-A-4 420 556).The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).

Hochmolekulare Farbkuppler sind beispielsweise 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 beschrieben. Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten monomeren Farbkupplern hergestellt. Sie können aber auch durch Polyaddition oder Polykondensation erhalten werden.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.

Die Einarbeitung der Kuppler oder anderer Verbindungen in Silberhalogenidemulsionsschichten kann in der Weise erfolgen, daß zunächst von der betreffenden Verbindung eine Lösung, eine Dispersion oder eine Emulsion hergestellt und dann die Gießlösung für die betreffende Schicht zugefügt wird. Die Auswahl des geeigneten Lösungs- oder Dispersionsmittels hängt von der jeweiligen Löslichkeit der Verbindung ab.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 the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.

Methoden zum Einbringen von in Wasser im wesentlichen unlöslichen Verbindungen durch Mahlverfahren sind beispielsweise in DE-A-2 609 741 und DE-A-2 609 742 beschrieben.Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-2 609 741 and DE-A-2 609 742.

Hydrophobe Verbindungen können auch unter Verwendung von hochsiedenden Lösungsmitteln, sogenannten Ölbildnern, in die Gießlösung eingebracht werden. Entsprechende Methoden sind beispielsweise in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 und EP-A-0 043 037 beschrieben.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.

Anstelle der hochsiedenden Lösungsmittel können Oligomere oder Polymere, sogenannte polymere Ölbildner Verwendung finden.Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.

Die Verbindungen können auch in Form beladener Latices in die Gießlösung eingebracht werden. Verwiesen wird beispielsweise auf DE-A-2 541 230, DE-A-2 541 274, DE-A-2 835 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, US-A-4 291 113.The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-2 541 230, DE-A-2 541 274, DE-A-2 835 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

Die diffusionsfeste Einlagerung anionischer wasserlöslicher Verbindungen (z.B. von Farbstoffen) kann auch mit Hilfe von kationischen Polymeren, sogenannten Beizpolymeren erfolgen.The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.

Geeignete Ölbildner sind z.B. Phthalsäurealkylester, Phosphorsäureester, Citronensäureester, Benzoesäureester, Alkylamide, Fettsäureester und Trimesinsäureester.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.

Farbfotografisches Material umfaßt typischerweise mindestens eine rotempfindliche Emulsionsschicht, mindestens eine grünempfindliche Emulsionsschicht und mindestens eine blauempfindliche Emulsionsschicht auf dem Träger. Die Reihenfolge dieser Schichten kann je nach Wunsch variiert werden. Gewöhnlich werden blaugrüne, purpurfarbene und gelbe Farbstoffe bildende Kuppler in die rot-, grün- bzw. blauempfindlichen Emulsionsschichten eingearbeitet. Es können jedoch auch unterschiedliche Kombinationenverwendetwerden.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 the support. The order of these layers can be varied as desired. Couplers which 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.

Jede der lichtempfindlichen Schichten kann aus einer einzigen Schicht bestehen oder auch zwei oder mehr Silberhalogenemulsionsteilschichten umfassen (DE-C-1 121 470). Dabei sind rotempfindliche Silberhalogenidemulsionsschichten dem Schichtträger häufig näher angeordnet als grünempfindliche Silberhalogenidemulsionsschichten und diese wiederum näher als blauempfindliche, wobei sich im allgemeinen zwischen grünempfindlichen Schichten und blauempfindlichen Schichten eine nicht lichtempfindliche gelbe Filterschicht befindet.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). There are red-sensitive Silberha logenide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

Bei geeignet geringer Eigenempfindlichkeit der grün- bzw. rotempfindlichen Schichten kann man unter Verzicht auf die Gelbfilterschicht andere Schichtanordnungen wählen, bei denen aufdem Träger z.B. die blauempfindlichen, dann die rotempfindlichen und schließlich die grünempfindlichen Schichten folgen.If the green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

Die in der Regel zwischen Schichten unterschiedlicher Spektralempfindlichkeit angeordneten nicht lichtempfindlichen Zwischenschichten können Mittel enthalten, die eine unerwünschte Diffusion von Entwickleroxidationsprodukten aus einer lichtempfindlichen in eine andere lichtempfindliche Schicht mit unterschiedlicher spektraler Sensibilisierung verhindern.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.

Liegen mehrere Teilschichten gleicher spektraler Sensibilisierung vor, so können sich diese hinsichtlich ihrer Zusammensetzung, insbesondere was Art und Menge der Silberhalogenidkörnchen betrifft, unterscheiden. Im allgemeinen wird die Teilschicht mit höherer Empfindlichkeit vom Träger entfernter angeordnet sein als die Teilschicht mit geringerer Empfindlichkeit. Teilschichten gleicher spektraler Sensibilisierung können zueinander benachbart oder durch andere Schichten, z.B. durch Schichten anderer spektraler Sensibilisierung, getrennt sein. So können z.B. alle hochempfindlichen und alle niedrigempfindlichen Schichten jeweils zu einem Schichtpaket zusammengefaßt sein (DE-A-1 958 709, DE-A-2 530 645, DE-A-2 622 922).If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sub-layer with 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. For example, 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).

Das fotografische Material kann weiterhin UV-Licht absorbierende Verbindungen, Weißtöner, Abstandshalter, Filterfarbstoffe, Formalinfänger und anderes enthalten.The photographic material may further contain compounds absorbing UV light, whiteners, spacers, filter dyes, formalin scavengers and others.

UV-Licht absorbierende Verbindungen sollen einerseits die Bildfarbstoffe vor dem Ausbleichen durch UV-reiches Tageslicht schützen und andererseits als Filterfarbstoffe das UV-Licht im Tageslicht bei der Belichtung absorbieren und so die Farbwiedergabe eines Films verbessern. Üblicherweise werden für die beiden Aufgaben Verbindungen unterschiedlicher Struktur eingesetzt. Beispiele sind arylsubstituierte Benzotriazolverbindungen (US-A-3 533 794), 4-Thiazolidonverbindungen (US-A-3 314 794 und 3 352 681), Benzophenonverbindungen (JP-A-2784/71), Zimtsäureesterverbindungen (US-A-3 705 805 und 3 707 375), Butadienverbindungen (US-A-4 015 229) oder Benzoxazolverbindungen (US-A-3 700 455).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-4,015,229) or benzoxazole compounds (US-A-3,700,455).

Es können auch ultraviolettabsorbierende Kuppler (wie Blaugrünkuppler des a-Naphtholtyps) und ultraviolettabsorbierende Polymere verwendet werden. Diese Ultraviolettabsorbentien können durch Beizen in einer speziellen Schicht fixiert sein.Ultraviolet absorbing couplers (such as a-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.

Für sichtbares Licht geeignete Filterfarbstoffe umfassen Oxonolfarbstoffe, Hemioxonolfarbstoffe, Styrolfarbstoffe, Merocyaninfarbstoffe, Cyaninfarbstoffe und Azofarbstoffe. Von diesen Farbstoffen werden Oxonolfarbstoffe, Hemioxonolfarbstoffe und Merocyaninfarbstoffe besonders vorteilhaft verwendet.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.

Geeignete Weißtöner sind z.B. in Research Disclosure Dezember 1978, Seite 22 ff, Referat 17 643, Kapitel V beschrieben.Suitable white toners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.

Bestimmte Bindemittelschichten, insbesondere die vom Träger am weitesten entfernte Schicht, aber auch gelegentlich Zwischenschichten, insbesondere, wenn sie während der Herstellung die vom Träger am weitesten entfernte Schicht darstellen, können fotografisch inerte Teilchen anorganischer oder organischer Natur enthalten, z.B. als Mattierungsmittel oder als Abstandshalter (DE-A-3 331 542, DE-A-3 424 893, Research Disclosure Dezember 1978, Seite 22 ff, Referat 17643, Kapitel XVI).Certain 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 17643, Chapter XVI).

Der mittlere Teilchendurchmesser der Abstandshalter liegt insbesondere im Bereich von 0,2 bis 10 um. Die Abstandshalter sind wasserunlöslich und können alkaliunlöslich oder alkalilöslich sein, wobei die alkalilöslichen im allgemeinen im alkalischen Entwicklungsbad aus dem fotografischen Material entfernt werden. Beispiele für geeignete Polymere sind Polymethylmethacrylat, Copolymere aus Acrylsäure und Methylmethacrylat sowie Hydroxypropylmethylcellulosehexahydrophthalat.The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. 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. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

Die Bindemittel des erfindungsgemäßen Materials, insbesondere wenn als Bindemittel Gelatine eingesetzt wird, werden mit geeigneten Härtern gehärtet, beispielsweise mit Härtern des Epoxidtyps, des Ethyleniumtyps, des Acryloyltyps oder des Vinylsulfontyps. Ebenso eignen sich Härter der Diazin-, Triazin-oder 1,2-Dihydrochinolin-Reihe.The binders of the material according to the invention, in particular if gelatin is used as the binder, are hardened with suitable hardeners, for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type. Hardeners of the diazine, triazine or 1,2-dihydroquinoline series are also suitable.

Vorzugsweise werden die Bindemittel des erfindungsgemäßen Materials mit Soforthärtern gehärtet.The binders of the material according to the invention are preferably hardened with instant hardeners.

Unter Soforthärtern werden Verbindungen verstanden, die geeignete Bindemittel so vernetzen, daß unmittelbar nach Beguß, spätestens nach 24 Stunden, vorzugsweise spätestens nach 8 Stunden die Härtung so weit abgeschlossen ist, daß keine weitere durch die Vernetzungsreaktion bedingte Änderung der Sensitometrie und der Quellung des Schichtverbandes auftritt. Unter Quellung wird die Differenz von Naßschichtdicke und Trockenschichtdicke bei der wäßrigen Verarbeitung des Films verstanden (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).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 caused by the crosslinking reaction and the swelling of the layer structure occurs . 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).

Bei diesen mit Gelatine sehr schnell reagierenden Härtungsmitteln handelt es sich z.B. um Carbamoylpyridiniumsalze, die mit freien Carboxylgruppen der Gelatine zu reagieren vermögen, so daß letztere mit freien Aminogruppen der Gelatine unter Ausbildung von Peptidbindungen und Vernetzung der Gelatine reagieren.These hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter also with free amino groups of the gelatin react to form peptide bonds and crosslink the gelatin.

Geeignete Beispiele für Soforthärter sind z.B. in der Europäischen Patentschrift 313 949 beschrieben.Suitable examples of instant hardeners are e.g. in European Patent 313,949.

Die erfindungsgemäßen Materialien werden nach den dafür empfohlenen Prozessen in üblicher Weise verarbeitet.The materials according to the invention are processed in the usual manner according to the processes recommended for this.

Beispiel 1example 1

Es werden die folgenden Lösungen jeweils mit demineralisiertem Wasser angesetzt:

Figure imgb0002
The following solutions are made up with demineralized water:
Figure imgb0002

Lösungen 2 und 3 werden bei 50 C im Laufe von 120 Minuten bei einem pAg von 7,7 gleichzeitig unter intensivem Rühren zur Lösung 1 gegeben. Es wird eine Silberchloridemulsion mit dem mittleren Teilchendurchmesser von 0,8 um erhalten. Das Gelatine/AgN03-Gewichtsverhältnis beträgt 0,18. Die Emulsion wird in bekannter Weise geflockt, gewaschen und mit so viel Gelatine redispergiert, daß das Gelatine/AgN03-Gewichtsverhältnis 1,0 beträgt. Die Emulsion enthält pro kg 1 Mol Silberhalogenid. Anschließend wird bei einem pH von 4,5 mit 3,5 µMol Goldchlorid/Mol Ag und 1,5 µMol Na2S203/MolAg optimal gereift. Nach der chemischen Reifung wird die Emulsion (Silberhalogenidzusammensetzung: AgCl0.99Br0.01) stabilisiert und für den blauen Spektralbereich sensibilisiert.Solutions 2 and 3 are simultaneously added to solution 1 at 50 ° C. over a period of 120 minutes at a pAg of 7.7 with vigorous stirring. A silver chloride emulsion with an average particle diameter of 0.8 µm is obtained. The gelatin / AgN0 3 weight ratio is 0.18. The emulsion is flocked in a known manner, washed and redispersed with enough gelatin that the gelatin / AgN0 3 weight ratio is 1.0. The emulsion contains 1 mol of silver halide per kg. The mixture is then optimally ripened at a pH of 4.5 with 3.5 μmol gold chloride / mol Ag and 1.5 μmol Na 2 S 2 0 3 / MolAg. After chemical ripening, the emulsion (silver halide composition: AgCl 0.99 Br 0.01 ) is stabilized and sensitized to the blue spectral range.

Danach wird die Emulsion mit einer Lösung des Gelbkupplers der Formel

Figure imgb0003

und dem Weißkuppler der Formel
Figure imgb0004

  • in Trikresylphosphat versetzt und auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier aufgetragen.
  • Die Schicht enthält pro m2
  • 0,63 g AgN03
  • 1,38 g Gelatine
  • 0,95 g Gelbkuppler
  • 0,2 g Weißkuppler
  • 0,29 g Trikresylphosphat.
  • Über diese Schicht wird eine Schutzschicht aus 0,2 g Gelatine und 0,3 g Härtungsmittel der Formel
    Figure imgb0005
    pro m2 gegossen. Das Material wird bildmäßig belichtet und nach dem Ektacolor RA 4-Prozeß verarbeitet.
Then the emulsion with a solution of the yellow coupler of the formula
Figure imgb0003
and the white coupler of the formula
Figure imgb0004
  • in tricresyl phosphate and applied to a substrate made of paper coated on both sides with polyethylene.
  • The layer contains per m 2
  • 0.63 g AgN0 3
  • 1.38 g gelatin
  • 0.95 g yellow coupler
  • 0.2 g white coupler
  • 0.29 g tricresyl phosphate.
  • A protective layer of 0.2 g of gelatin and 0.3 g of hardening agent of the formula is applied over this layer
    Figure imgb0005
    cast per m 2 . The material is exposed imagewise and processed using the Ektacolor RA 4 process.

Beispiel 2Example 2

Die Emulsion wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit dem Unterschied, daß bei der chemischen Reifung vor der Thiosulfat-Zugabe 4,5 mg Diphenylindolyldisulfid als 0,1 gew.-%ige acetonische Lösung zugesetzt werden.The emulsion is prepared and processed as described in Example 1, but with the difference that during chemical ripening, 4.5 mg of diphenylindolyl disulfide are added as a 0.1% by weight acetone solution before the thiosulfate is added.

Beispiel 3Example 3

Die Emulsion wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit dem Unterschied, daß bei der chemischen Reifung vor der Thiosulfat-Zugabe 225 mg Diphenylindolyldisulfid zugesetzt werden.The emulsion is prepared and processed as described in Example 1, but with the difference that 225 mg of diphenylindolyl disulfide are added during chemical ripening before the addition of thiosulfate.

Die sensitomethschen Ergebnisse sind in Tabelle 1 dargestellt.

Figure imgb0006
The sensitometric results are shown in Table 1.
Figure imgb0006

Beispiel 4Example 4

Es werden die folgenden Lösungen jeweils mit demineralisiertem Wasser angesetzt:

Figure imgb0007
The following solutions are made up with demineralized water:
Figure imgb0007

Lösungen 2 und 3 werden bei 55 ° C im Laufe von 60 Minuten bei einem pAg von 7,8 gleichzeitig unter intensivem Rühren zur Lösung 1 gegeben. Die Emulsion wird in bekannter Weise geflockt, gewaschen und unter Zusatz von Gelatine, Phenol (als Konservierungsmittel) und Wasser redispergiert. Die Emulsion enthält pro kg 0,9 Mol Silberhalogenid. Anschließend wird unter Zusatz von 10 µMol HAuC14/Mol Ag und 20 µMol Na2S203/Mol Ag 120 Minuten bei 52°C gereift. Danach wird die Emulsion (Silberhalogenidzusammensetzung: AgClo,5Bro,5) auf einem beidseitig mit Polyethylen beschichteten Papierträger unter Zusatz von Sensibilisatoren, Stabilisatoren, Weichmacher-Latex, optischen Aufhellern, Entwicklersubstanzen und Härtungsmitteln vergossen. Das Material wird bildmäßig belichtet und nach dem Rezept AGFA 100 verarbeitet.Solutions 2 and 3 are simultaneously added to solution 1 at 55 ° C. in the course of 60 minutes at a pAg of 7.8 with vigorous stirring. The emulsion is flocculated in a known manner, washed and redispersed with the addition of gelatin, phenol (as a preservative) and water. The emulsion contains 0.9 mol of silver halide per kg. The mixture is then ripened at 52 ° C. for 120 minutes with the addition of 10 μmol HAuC1 4 / mol Ag and 20 μmol Na 2 S 2 0 3 / mol Ag. Then the emulsion (silver halide composition: AgCl o , 5 Br o , 5 ) is poured onto a paper support coated on both sides with polyethylene with the addition of sensitizers, stabilizers, plasticizer latex, optical brighteners, developer substances and hardening agents. The material is exposed imagewise and processed according to the AGFA 100 recipe.

Beispiel 5Example 5

Die Emulsion wird hergestellt und verarbeitet wie in Beispiel 4 beschrieben, jedoch mit dem Unterschied, daß bei der chemischen Reifung vor der Zugabe der Reifsubstanzen 160 mg Diphenylindolyldisulfid zugesetzt werden.The emulsion is prepared and processed as described in Example 4, but with the difference that in chemical ripening, 160 mg of diphenylindolyl disulfide before the addition of the ripening substances be added.

Beispiel 6Example 6

Die Emulsion wird hergestellt und verarbeitet wie in Beispiel 4 beschrieben. Die Messung der sensitometrischen Daten erfolgt jedoch erst nach einer zweitägigen Lagerung bei 60 ° C.The emulsion is prepared and processed as described in Example 4. However, the sensitometric data are only measured after a two-day storage at 60 ° C.

Beispiel 7Example 7

Die Emulsion wird hergestellt und verarbeitet wie in Beispiel 5 beschrieben. Die Messung der sensitometrischen Daten erfolgt jedoch erst nach einer zweitägigen Lagerung bei 60 ° C.The emulsion is prepared and processed as described in Example 5. However, the sensitometric data are only measured after a two-day storage at 60 ° C.

Beispiel 8Example 8

Die Emulsion wird hergestellt und verarbeitet wie in Beispiel 4 beschrieben, jedoch erfolgte nach bildmäßiger Belichtung eine zusätzliche diffuse Belichtung durch Amber-Filter (entspricht dem Norm-Entwurf ISO/DIS 8374).The emulsion is produced and processed as described in Example 4, but after image-wise exposure, an additional diffuse exposure was carried out using amber filters (corresponds to the draft standard ISO / DIS 8374).

Beispiel 9Example 9

Die Emulsion wird hergestellt und verarbeitet wie in Beispiel 5 beschrieben, jedoch erfolgte nach bildmäßiger Belichtung eine zusätzliche diffuse Belichtung durch Amber-Filter (entspricht dem Norm-Entwurf ISO/DIS 8374).The emulsion is produced and processed as described in Example 5, but after image-wise exposure, an additional diffuse exposure was carried out using amber filters (corresponds to the draft standard ISO / DIS 8374).

Die sensitometrischen Ergebnisse sind in Tabelle 2 dargestellt.

Figure imgb0008
The sensitometric results are shown in Table 2.
Figure imgb0008

Claims (5)

1. Fotografische Silberhalogenidemulsion, dadurch gekennzeichnet, daß die Emulsion 10-7 bis 10-3 Mol/Mol Silber einer Verbindung der Formel (I)
Figure imgb0009
worin R1 H oder Alkyl, R2 Alkyl, Benzyl, Phenyl oder substituiertes Phenyl, R3, R4 H, Alkyl, Alkoxy, Halogen oder Nitro bedeuten, enthält. 1. Photographic silver halide emulsion, characterized in that the emulsion 10 -7 to 10- 3 mol / mol of silver of a compound of formula (I)
Figure imgb0009
wherein R 1 is H or alkyl, R 2 is alkyl, benzyl, phenyl or substituted phenyl, R 3 , R 4 H, alkyl, alkoxy, halogen or nitro mean contains. 2. Fotografische Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß die Emulsion mit 10-9 bis 10-4 Mol/Mol Ag Rh3+- und/oder Ir4+-lonen dotiert ist.2. Photographic silver halide emulsion according to claim 1, characterized in that the emulsion is doped with 10- 9 to 10- 4 mol / mol Ag Rh 3 + - and / or Ir 4+ ions. 3. Fotografische Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß 2·10-6 bis 2·10-4 Mol Goldverbindung und 10-6 bis 10-4 Mol Schwefelverbindung pro Mol Silber zur Reifung der Emulsion eingesetzt werden.3. Photographic silver halide emulsion according to claim 1, characterized in that 2 · 10 -6 to 2 · 10 -4 mol of gold compound and 10- 6 to 10- 4 mol of sulfur compound per mol of silver are used to ripen the emulsion. 4. Fotografische Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß die Emulsion eine Zusammensetzung von AgCl0.15Br0.85 bis AgCl0.999Br0.001 hat.4. Photographic silver halide emulsion according to claim 1, characterized in that the emulsion has a composition of AgCl 0.15 Br 0.85 to AgCl 0.999 Br 0.001 . 5. Fotografisches Material mit einem Träger und wenigstens einer lichtempfindlichen Silberhalogenidemulsionsschicht, dadurch gekennzeichnet, daß die Silberhalogenidemulsionsschicht eine Silberhalogenidemulsion nach Anspruch 1 enthält.5. Photographic material with a support and at least one light-sensitive silver halide emulsion layer, characterized in that the silver halide emulsion layer contains a silver halide emulsion according to claim 1.
EP92108735A 1991-06-06 1992-05-23 Photographic silver halide emulsion Expired - Lifetime EP0517053B1 (en)

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EP0566080A2 (en) * 1992-04-16 1993-10-20 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364754A (en) * 1992-04-16 1994-11-15 Eastman Kodak Company Silver halide photographic emulsions precipitated in the presence of organic dichalcogenides
DE19507914A1 (en) * 1995-03-07 1996-09-12 Agfa Gevaert Ag Stabilisation of colour photographic silver halide
US5851753A (en) * 1995-10-13 1998-12-22 Konica Corporation Silver halide photographic light-sensitive material
JPH09311399A (en) * 1996-05-24 1997-12-02 Konica Corp Silver halide photographic sensitive material and method for photographing by using same and processing same
US5843632A (en) * 1997-06-27 1998-12-01 Eastman Kodak Company Photothermographic composition of enhanced photosensitivity and a process for its preparation
US6767200B2 (en) * 2001-09-28 2004-07-27 Mcneil-Ppc, Inc. Systems, methods and apparatuses for manufacturing dosage forms

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2226877A1 (en) * 1971-06-02 1972-12-28 Fuji Photo Film Co. Ltd., Ashigara Kanagawa (Japan) Process for the preparation of silver halide photographic emulsions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2440110A (en) * 1944-10-06 1948-04-20 Gen Aniline & Film Corp Stabilized silver halide emulsions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2226877A1 (en) * 1971-06-02 1972-12-28 Fuji Photo Film Co. Ltd., Ashigara Kanagawa (Japan) Process for the preparation of silver halide photographic emulsions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEM. PHARM. BULL. Bd. 21, Nr. 12, 28. Mai 1973, Seiten 2739 - 2748; T. HINO ET AL: 'Preparation of 3-Substituted 2-Indolinethiones via Diindolyl Disulfides. The Reaction of 3-Substituted Indoles with Sulfur Monochloride' *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0566080A2 (en) * 1992-04-16 1993-10-20 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
EP0566080A3 (en) * 1992-04-16 1995-01-04 Eastman Kodak Co Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides.

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DE4118542A1 (en) 1992-12-10
DE59200097D1 (en) 1994-04-28
EP0517053B1 (en) 1994-03-23
US5229264A (en) 1993-07-20
JPH05181224A (en) 1993-07-23

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