EP0317886B1 - Gradation-variable black and white paper - Google Patents

Gradation-variable black and white paper Download PDF

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Publication number
EP0317886B1
EP0317886B1 EP88119074A EP88119074A EP0317886B1 EP 0317886 B1 EP0317886 B1 EP 0317886B1 EP 88119074 A EP88119074 A EP 88119074A EP 88119074 A EP88119074 A EP 88119074A EP 0317886 B1 EP0317886 B1 EP 0317886B1
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EP
European Patent Office
Prior art keywords
emulsion
gradation
paper
variable
mol
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EP88119074A
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German (de)
French (fr)
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EP0317886A2 (en
EP0317886A3 (en
Inventor
Walter Dr. Pätzold
Helmut Dr. Kampfer
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • 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
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • 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
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • G03C2001/03564—Mixed grains or mixture of emulsions

Definitions

  • the invention relates to a variable-grade black-and-white paper (BW paper) which contains at least two silver halide emulsions which are mixed prior to casting and which are sensitive to different spectral ranges, a special stabilizer being added to at least one emulsion.
  • BW paper black-and-white paper
  • Gradation-variable light-sensitive silver halide materials contain emulsions that are light-sensitive for different spectral ranges. Depending on the composition of the copying light, a harder or softer gradation is achieved. The emulsions are usually mixed before pouring so that only one layer has to be poured. There is a danger that sensitization occurs, ie that the sensitizing dye is desorbed from the silver halide grains of an emulsion and adsorbed on the grains of an unsensitized, blue-sensitive emulsion. This is undesirable, since such a differentiated exposure by changing the copying light no longer leads to the desired result. Under unfavorable conditions, the process of sensitization is not limited to the casting solution, but can also occur on the finished material, for example under the influence of moisture, heat or both.
  • the object of the invention was therefore to provide a gradation-variable SW paper in which these disadvantages do not occur.
  • Suitable heterocyclic rings are 5- and 6-membered rings which contain one to three heteroatoms from the O, S, Se and N series and can be benzo- or naphthocondensed. Examples are oxazole, thiazole, selenazole, imidazole, tetrazole, triazoles, pyrimidine as well their benzo and naphtho-fused derivatives which are substituted by sulfo, carboxy, halogen, C1-C4-alkyl, aryl, especially phenyl, sulfophenyl, carboxyphenyl, C1-C4-alkylcarbonylamino, C1-C4-alkylaminosulfonyl or arylaminosulfonyl, especially phenylaminosulfonyl and chlorophenylaminosulfonyl can.
  • R1 and R2 are the remaining members of a benzo or naphtho radical substituted by at least one sulfo group, which may optionally contain further substituents.
  • R1 and R2 are the remaining members of a benzo or naphtho radical substituted by one or two sulfo groups, which can be further substituted by C1-C4-alkyl or halogen.
  • the sulfonic acid and mercapto groups can also be present in the form of their salts, especially their alkali or ammonium salts. Suitable examples are: The emulsion with an absorption maximum between 480 and 580 nm is produced by conventional spectral sensitization with green-sensitive sensitizers.
  • the emulsion with an absorption maximum below 480 nm is either an unsensitized silver halide emulsion, the intrinsic sensitivity of which is in the range given, absorptions below 360 nm are of no interest, since the absorption of the gelatin or an emulsion that contains a blue-sensitive sensitizer lies after shorter wavelengths.
  • the green and blue-sensitive partial emulsions can be mixed in a weight ratio of 1.5: 1 to 1:10, preferably 1: 1 to 1: 3, based on their silver content.
  • the emulsions are preferably silver chloride bromide emulsions with 20 to 80 mol% chloride, 20 to 80 mol% bromide and 0 to 5 mol% iodide.
  • the average grain size is in particular from 0.2 to 0.6 ⁇ m, the silver halide grains being cubic to octahedral.
  • the average grain size can be between 0.2 to 0.6 ⁇ m, preferably 0.4 to 0.5 ⁇ m.
  • the silver halide crystals can be doped with Rh3+, Ir4+, Cd2+, Zn2+, Pb2+.
  • the emulsion can be desalted in the customary manner (dialysis, flocculation and redispersion, ultrafiltration).
  • Chemical sensitization can take place through unstable sulfur compounds (e.g. thiosulfate, diacetyl-thiourea), through gold-sulfur ripening or reduction ripening. Chemical sensitization can be carried out with the addition of Ir, Rh, Pb, Cd, Hg, Au.
  • unstable sulfur compounds e.g. thiosulfate, diacetyl-thiourea
  • gold-sulfur ripening or reduction ripening e.g., gold-sulfur ripening or reduction ripening.
  • the binder is an essential component of the at least one light-sensitive layer in addition to the silver halide.
  • 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 generally 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 silver halide present as a light-sensitive component in the photographic material can be predominantly compact crystals, which are e.g. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals may preferably also be present, the average ratio of diameter to thickness of which is preferably greater than 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 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 doping of the individual grain areas, being different.
  • the grain size distribution can be both homodisperse and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
  • the emulsions can also contain organic silver salts, for example 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 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 water-soluble silver salts and the halides are optionally carried out 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 an excess of 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, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • the photographic emulsions can contain compounds for preventing the formation of fog or for stabilizing the photographic function during production, storage or photographic processing, in particular also in the layer which is sensitive in the range from 480 to 580 nm.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from 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.
  • 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
  • Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
  • these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • a water-solubilizing group for example a carboxyl group or sulfo group.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can be surface-active Contain 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 (e.g. acceleration of development, high contrast, sensitization, etc.).
  • Chemical sensitization can take place through unstable sulfur compounds (e.g. thiosulfate, diacetyl-thiourea), through gold-sulfur ripening or reduction ripening. Chemical sensitization can be carried out with the addition of Ir, Rh, Pb, Cd, Hg, Au, as well as the addition of optical sensitizers or stabilizers.
  • unstable sulfur compounds e.g. thiosulfate, diacetyl-thiourea
  • Chemical sensitization can be carried out with the addition of Ir, Rh, Pb, Cd, Hg, Au, as well as the addition of optical sensitizers or stabilizers.
  • the photographic material may further contain UV light absorbing compounds, whites, spacers, 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 Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. Nos. A3,314,794 and 3,352,681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US Pat. No. 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.
  • Suitable whiteners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.
  • 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 materials according to the invention are processed in the usual manner according to processes recommended for this.
  • Grain diameter 0.42 microns is desalted in a known manner and matured after the addition of 20 microns thiosulfate / mole AgNo3 under sensitometric control to an optimal sensitivity-fog ratio.
  • the emulsion contains 100 g of AgNO3 in 1 kg of emulsion.
  • Green-sensitized partial emulsion 300 g of the emulsion are optically sensitized for the green spectral range by adding 37 mg of the sensitizer SE 18 and stabilized by adding 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine per kg of emulsion.
  • Unsensitized partial emulsion 700 g of the emulsion are stabilized by adding 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine.
  • the partial emulsions are mixed; a part is cast on an opaque support with the addition of a gelatin hardening agent (test 1A). Another part of the mixture is kept at 40 ° C. for 4 hours and then poured with the addition of a gelatin hardening agent (experiment 1B).
  • Emulsion preparation and sensitization for the spectral range from 480 to 580 nm is carried out according to Example 1.
  • Unsensitized partial emulsion This part of the emulsion is stabilized as in Example 1 with 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine and additionally with 200 mg of Stabilizer III per kg of emulsion.
  • the partial emulsions are mixed and poured according to Example 1 (tests 2A and 2B).
  • Emulsion preparation and sensitization for the spectral range from 480 to 580 nm correspond to Example 1, but 250 g of an emulsion of 60 mol% AgCl, 39.5 mol% AgBr and 0.5 mol% AgI are used.
  • Blue-sensitized partial emulsion 250 mg of the unsensitized emulsion are mixed with 20 mg of sensitizer BS6 and 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine.
  • Unsensitized partial emulsion 500 g of the unsensitized emulsion are mixed with 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine and 160 mg of stabilizer I.
  • a sample of the material is exposed behind a yellow filter and a step part.
  • a second sample is exposed behind a purple filter and a step part.
  • the developer is then developed with a developer customary for SW paper (e.g. Agfa 100) and the density of the steps is measured.
  • Log ER is determined from the density curve in accordance with ANSI standard PH 2.2-1966 (Table 1).
  • Part of the material (1A, 2A, 3A) is subjected to an artificial aging by storage for 2 days in a warm, humid atmosphere at 45 ° C. and 65% rel. Humidity (1C, 2C, 3C).
  • Example 2 Analogously to Example 1, the following emulsions of the specified composition and grain size are prepared and chemically ripened. Each emulsion is divided into 2 equal parts, of which the first partial emulsion is sensitized with the spectral sensitizer in the range between 480 and 580 nm and the second partial emulsion is mixed with the stabilizer according to the invention. Then the two partial emulsions are mixed and cast as usual on PE paper base with an application of 1.4 g of silver per m2. These samples according to the invention are designated A.
  • Samples B differ from A in that the stabilizer in the second partial emulsion is omitted.
  • Samples C contain the spectral sensitizer evenly distributed over all emulsion crystals in the same concentration per m2 as for samples A and B.
  • the samples are then subjected to sensitometric exposure behind a yellow and a purple filter with the spectral characteristics "Gb" and "Pp" shown in FIG. 1. It is then developed in Agfa-Neutol paper developer and log ER determined.
  • a silver chloride emulsion with 70 mol% chloride and 30 mol% bromide and an average grain size of 0.3 ⁇ is produced and chemically ripened as described in Example 1.
  • the emulsion is then divided into two equal parts as described in Example 4.
  • the first partial emulsion is sensitized with 75 ⁇ mol per mole Ag of the sensitizer dye SE 6.
  • the second partial emulsion is sensitized with a blue sensitizer BS as indicated in Table 6 and stabilized with 240 mg of stabilizer III.
  • the part emulsions After the part emulsions have been mixed, they are poured onto PE paper substrates. As in Example 4, the layers are subjected to sensitometric exposure behind a yellow and purple filter.
  • the blue sensitivity (column 5) can be increased considerably by adding the blue sensitizers without losing the gamma differentiation according to the invention.

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Description

Die Erfindung betrifft ein gradationsvariables Schwarz-Weiß-Papier (SW-Papier), das mindestens zwei Silberhalogenidemulsionen enthält, die vor dem Vergießen gemischt werden und die für unterschiedliche Spektralbereiche empfindlich sind, wobei wenigstens einer Emulsion ein spezieller Stabilisator zugesetzt wird.The invention relates to a variable-grade black-and-white paper (BW paper) which contains at least two silver halide emulsions which are mixed prior to casting and which are sensitive to different spectral ranges, a special stabilizer being added to at least one emulsion.

Gradationsvariable lichtempfindliche Silberhalogenidmaterialien enthalten Emulsionen, die für verschiedene Spektralbereiche lichtempfindlich sind. Je nach Zusammensetzung des Kopierlichtes erzielt man härtere oder weichere Gradation. Die Emulsionen werden üblicherweise vor dem Vergießen gemischt, damit nur eine Schicht gegossen werden muß. Dabei besteht die Gefahr, daß Umsensibilierung eintritt, d.h., daß Sensibilierungsfarbstoff von den Silberhalogenidkörnern einer Emulsion desorbiert und an Körnern einer unsensibilisierten, blauempfindlichen Emulsion adsorbiert wird. Dies ist unerwünscht, da so eine differenzierte Belichtung durch Änderung des Kopierlichtes nicht mehr zu dem gewünschten Ergebnis führt. Unter ungünstigen Bedingungen ist der Vorgang der Umsensibilisierung nicht auf die Gießlösung beschränkt, sondern kann auch am fertigen Material auftreten, z.B. unter Einwirkung von Feuchte, Wärme oder beidem.Gradation-variable light-sensitive silver halide materials contain emulsions that are light-sensitive for different spectral ranges. Depending on the composition of the copying light, a harder or softer gradation is achieved. The emulsions are usually mixed before pouring so that only one layer has to be poured. There is a danger that sensitization occurs, ie that the sensitizing dye is desorbed from the silver halide grains of an emulsion and adsorbed on the grains of an unsensitized, blue-sensitive emulsion. This is undesirable, since such a differentiated exposure by changing the copying light no longer leads to the desired result. Under unfavorable conditions, the process of sensitization is not limited to the casting solution, but can also occur on the finished material, for example under the influence of moisture, heat or both.

Um die Umsensibilierung zu vermeiden, müssen aufwendige Vorkehrungen getroffen werden, beispielsweise bei der Lagerung des Fertigmaterials oder durch Verkürzen der Standzeit der fertigen Gießlösung. Da diese negativen Einflüsse nicht immer durch den Produzenten ausgeschaltet werden können, hat es nicht an Versuchen gefehlt, Methoden zur Vermeidung der Umsensibilisierung zu entwickeln. So wurde vorgeschlagen, überschüssigen Sensibilsierungsfarbstoff zu entfernen (DL-PS 7210), beim Mischen und Gießen der Gießlösung bestimmte kritische Temperaturen nicht zu überschreiten (US-PS 2 367 508), längere Stehzeiten der Gießlösungen zu vermeiden (GB-PS 540 451, DE-OS 2 426 676), den Gießlösungen Metallverbindungen zur Verhinderung der Diffusion der Sensibilisierungsfarbstoffe zuzusetzen (US-PS 2 336 260) oder die unterschiedlich sensibilisierten bzw. unsensibilisierten Emulsionen nicht zu mischen, sondern getrennt übereinander zu gießen (GB-PS 541 515, FR-PS 2 251 837 und DE-A-30 28 167).In order to avoid sensitization, elaborate precautions have to be taken, for example when storing the finished material or by shortening the service life of the finished casting solution. Since these negative influences cannot always be eliminated by the producer, there has been no lack of attempts to develop methods for avoiding sensitization. It has been proposed to remove excess sensitizing dye (DL-PS 7210), not to exceed certain critical temperatures when mixing and pouring the casting solution (US Pat. No. 2,367,508), to avoid longer standing times of the casting solutions (GB-PS 540 451, DE -OS 2 426 676) to add metal compounds to the casting solutions to prevent the diffusion of the sensitizing dyes (US Pat. No. 2,336,260) or not to mix the differently sensitized or unsensitized emulsions, but to pour them separately over one another (GB-PS 541 515, FR -PS 2 251 837 and DE-A-30 28 167).

Alle diese Maßnahmen haben nicht zu einer befriedigenden Lösung des Problems geführt, da entweder die Umsensibilisierung bei der Lagerung des fertigen Materials nicht ausgeschlossen werden konnte oder die Herstellung des Materials durch den Mehrfachguß wesentlich aufwendiger wurde.All of these measures have not led to a satisfactory solution to the problem, as either sensitization could not be excluded in the storage of the finished material or the production of the material by multiple casting was much more complex.

Aufgabe der Erfindung war daher die Bereitstellung eines gradationsvariablen SW-Papiers, bei dem diese Nachteile nicht auftreten.The object of the invention was therefore to provide a gradation-variable SW paper in which these disadvantages do not occur.

Es wurde nun gefunden, daß man diese Aufgabe mit einem gradationsvariablem SW-Papier mit wenigstens einer Silberhalogenidemulsionsschicht lösen kann, wobei man mindestens zwei lichtempfindliche Silberhalogenidemulsionen von denen die eine im Bereich von 480 bis 580 nm, vorzugsweise 500 bis 550 nm, und die andere unterhalb von 480 nm ihr Absorotionsmaximum hat, zu einer Gießlösung mischt und diese Gießlösung auf den Träger aufbringt, wobei die Emulsion, die unterhalb 480 nm ihr Absorptionsmaximum hat, eine Verbindung der Formel

Figure imgb0001

enthält, worin

X
die restlichen Glieder eines gegebenenfalls weitere Substituenten enthaltenden, gegebenenfalls benzo- oder naphthokondensierten Heterocyclus dartellt.
It has now been found that this object can be achieved with a variable-grade SW paper with at least one silver halide emulsion layer, at least two light-sensitive silver halide emulsions, one in the range from 480 to 580 nm, preferably 500 to 550 nm, and the other below of 480 nm has its absorption maximum, mixes into a casting solution and applies this casting solution to the support, the emulsion, which has its absorption maximum below 480 nm, a compound of the formula
Figure imgb0001
contains what
X
the remaining members of a heterocycle optionally containing further substituents, optionally benzo- or naphthocondensed.

Als heterocyclische Ringe kommen 5- und 6-gliedrige Ringe infrage, die ein- bis drei Heteroatome aus der Reihe O, S, Se und N enthalten und benzo- oder naphthokondensiert sein können. Beispiele sind Oxazol, Thiazol, Selenazol, Imidazol, Tetrazol, Triazole, Pyrimidin sowie deren benzo- und napthokondensierten Derivate, die durch Sulfo, Carboxy, Halogen, C₁-C₄-Alkyl, Aryl, insbesondere Phenyl, Sulfophenyl, Carboxyphenyl, C₁-C₄-Alkylcarbonylamino, C₁-C₄-Alkylaminosulfonyl oder Arylaminosulfonyl, insbesondere Phenylaminosulfonyl und Chlorphenylaminosulfonyl substituiert sein können.Suitable heterocyclic rings are 5- and 6-membered rings which contain one to three heteroatoms from the O, S, Se and N series and can be benzo- or naphthocondensed. Examples are oxazole, thiazole, selenazole, imidazole, tetrazole, triazoles, pyrimidine as well their benzo and naphtho-fused derivatives which are substituted by sulfo, carboxy, halogen, C₁-C₄-alkyl, aryl, especially phenyl, sulfophenyl, carboxyphenyl, C₁-C₄-alkylcarbonylamino, C₁-C₄-alkylaminosulfonyl or arylaminosulfonyl, especially phenylaminosulfonyl and chlorophenylaminosulfonyl can.

Bevorzugt sind Verbindungen der Formel

Figure imgb0002

worin R₁ und R₂ die restlichen Glieder eines durch wenigstens eine Sulfogruppe substituierten Benzo- oder Naphthorestes sind, der gegebenenfalls weitere Substituenten enthalten kann.Compounds of the formula are preferred
Figure imgb0002
wherein R₁ and R₂ are the remaining members of a benzo or naphtho radical substituted by at least one sulfo group, which may optionally contain further substituents.

Vorzugsweise sind R₁ und R₂ die restlichen Glieder eines durch eine oder zwei Sulfogruppen substituierten Benzo- oder Naphthorestes, der durch C₁-C₄-Alkyl oder Halogen weiter substituiert sein kann. Die Sulfonsäure- und die Mercaptogruppen können auch in Form ihrer Salze, insbesondere ihrer Alkali- oder Ammoniumsalze vorliegen. Geeignete Beispiele sind:

Figure imgb0003
Figure imgb0004
Figure imgb0005
Die Emulsion mit einem Absorptionsmaximum zwischen 480 und 580 nm wird durch übliche spektrale Sensibilisierung mit grünempfindlichen Sensibilisatoren hergestellt.Preferably R₁ and R₂ are the remaining members of a benzo or naphtho radical substituted by one or two sulfo groups, which can be further substituted by C₁-C₄-alkyl or halogen. The sulfonic acid and mercapto groups can also be present in the form of their salts, especially their alkali or ammonium salts. Suitable examples are:
Figure imgb0003
Figure imgb0004
Figure imgb0005
The emulsion with an absorption maximum between 480 and 580 nm is produced by conventional spectral sensitization with green-sensitive sensitizers.

Die Emulsion mit einem Absorptionsmaximum unterhalb 480 nm ist entweder eine unsensibilisierte Silberhalogenidemulsion, deren Eigenempfindlichkeit in dem angegebenen Bereich liegt, wobei Absorptionen unterhalb 360 nm ohne Interesse sind, da von hier nach kürzeren Wellenlängen die Absorption der Gelatine liegt, oder eine Emulsion, die einen blauempfindlichen Sensibilisator enthält.The emulsion with an absorption maximum below 480 nm is either an unsensitized silver halide emulsion, the intrinsic sensitivity of which is in the range given, absorptions below 360 nm are of no interest, since the absorption of the gelatin or an emulsion that contains a blue-sensitive sensitizer lies after shorter wavelengths.

Die grün- und blauempfindlichen Teilemulsionen können im Gewichtsverhältnis 1,5:1 bis 1:10, vorzugsweise 1:1 bis 1:3, bezogen auf ihren Silbergehalt, abgemischt werden.The green and blue-sensitive partial emulsions can be mixed in a weight ratio of 1.5: 1 to 1:10, preferably 1: 1 to 1: 3, based on their silver content.

Bei den Emulsionen handelt es sich vorzugsweise um Silberchloridbromidemulsionen mit 20 bis 80 Mol-% Chlorid, 20 bis 80 Mol-% Bromid und 0 bis 5 Mol-% Iodid. Die mittlere Korngröße liegt insbesondere bei 0,2 bis 0,6 µm, wobei die Silberhalogenidkörner kubisch bis oktaedrisch sind.The emulsions are preferably silver chloride bromide emulsions with 20 to 80 mol% chloride, 20 to 80 mol% bromide and 0 to 5 mol% iodide. The average grain size is in particular from 0.2 to 0.6 μm, the silver halide grains being cubic to octahedral.

Für erfindungsgemäßes Material geeignete fotografische Emulsionen können durch "Kippen" (=schnelles ungesteuertes Mischen der Reaktionslösungen), single-jet-Fällung, double-jet-Fällung oder Konvertierungsverfahren hergestellt werden.Photographic emulsions suitable for the material according to the invention can be prepared by “tilting” (= rapid, uncontrolled mixing of the reaction solutions), single-jet precipitation, double-jet precipitation or conversion processes.

Die mittlere Korngröße kann zwischen 0,2 bis 0,6 µm betragen, bevorzugt 0,4 bis 0,5 µm.The average grain size can be between 0.2 to 0.6 μm, preferably 0.4 to 0.5 μm.

Die Silberhalogenidkristalle können mit Rh³⁺, Ir⁴⁺, Cd²⁺, Zn²⁺, Pb²⁺ dotiert sein.The silver halide crystals can be doped with Rh³⁺, Ir⁴⁺, Cd²⁺, Zn²⁺, Pb²⁺.

Die Entsalzung der Emulsion kann auf übliche Weise erfolgen (Dialyse, Flocken und Redispergieren, Ultrafiltration).The emulsion can be desalted in the customary manner (dialysis, flocculation and redispersion, ultrafiltration).

Die chemische Sensibilisierung kann durch labile Schwefelverbindungen (z.B. Thiosulfat, Diacetyl-thioharnstoff), durch Gold-Schwefelreifung oder Reduktionsreifung erfolgen. Die chemische Sensibilisierung kann unter Zusatz von Ir, Rh, Pb, Cd, Hg, Au erfolgen.Chemical sensitization can take place through unstable sulfur compounds (e.g. thiosulfate, diacetyl-thiourea), through gold-sulfur ripening or reduction ripening. Chemical sensitization can be carried out with the addition of Ir, Rh, Pb, Cd, Hg, Au.

Zur Erzeugung der Epfindlichkeit im Bereich von 480-580 sind Cyanin- und Merocyaninfarbstoffe geeignet, wie sie in der Monographie von F, M, Hamer, The Cyanine Dyes and Related Compounds, 1964, John Wiley & Sons, beschrieben sind. Geeignet sind beispielsweise Farbstoffe der folgenden Formeln:

Figure imgb0006

worin

X, Y
O, N-R₇
U, V
CH₂, C(R₇)₂, O, N-R₇, S
Z
S, Se, -CH=CH-
R₃, R₄
CH₃, C₂H₅, OCH₃, Halogen, CN, SO₂R₅, Carbalkoxy, Sulfonamido, sowie - mit n bzw. m = 2 - Ergänzung zum anellierten Benzring
R₅, R₆
H, CH₃, C₂H₅
R₇, R₈
CH₃, C₂H₅
n, m
0-2
W₁. W₂
C₁-C₄-Alkyl, gegebenenfalls substiutiert mit Hydroxy, Carboxy oder Sulfo und
Q
die zur Ergänzung eines Rhodanin-, Thiohydantoin-, Thiooxazolidon- oder Thiobarbitursäure-Rings erforderlichen Ringglieder bedeuten.
Cyanine and merocyanine dyes, as described in the monograph by F, M, Hamer, The Cyanine Dyes and Related Compounds, 1964, John Wiley & Sons, are suitable for producing the sensitivity in the range of 480-580. For example, dyes of the following formulas are suitable:
Figure imgb0006
wherein
X, Y
O, N-R₇
U, V
CH₂, C (R₇) ₂, O, N-R₇, S
Z.
S, Se, -CH = CH-
R₃, R₄
CH₃, C₂H₅, OCH₃, halogen, CN, SO₂R₅, carbalkoxy, sulfonamido, and - with n or m = 2 - supplement to the fused benz ring
R₅, R₆
H, CH₃, C₂H₅
R₇, R₈
CH₃, C₂H₅
n, m
0-2
W₁. W₂
C₁-C₄-alkyl, optionally substituted with hydroxy, carboxy or sulfo and
Q
mean the ring members required to complete a rhodanine, thiohydantoin, thiooxazolidone or thiobarbituric acid ring.

Besonders geeignet sind beispielsweise folgende Farbstoffe:

Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Obwohl der zweite Emulsionsanteil mit einer spektralen Empfindlichkeit < 480 nm auch ohne Zusatz eines spektralen Sensibilisators erfindungsgemäß verwendet werden kann, ist es doch von Vorteil, diesen Emulsionsteil in der Empfindlichkeit bei Wellenlängen < 480 nm durch Zusatz eines geeigneten Sensibilisierungsfarbstoffs zu erhöhen. Zu diesem Zweck sind beispielsweise Farbstoffe der folgenden Formeln geeignet:
Figure imgb0012
worin

P
die zur Ergänzung eines gegebenenfalls benzo-anellierten heterocyclischen Fünfrings erforderlichen Glieder
R, T
O, S, N-R₇
R₉, R₁₀
CH₃, CH₃O, Halogen und - sofern R oder T O ist - Phenyl bedeuten
und
Q, W₁, W₂, n, m
die oben angegebene Bedeutung haben.
The following dyes are particularly suitable, for example:
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Although the second emulsion portion with a spectral sensitivity <480 nm can also be used according to the invention without the addition of a spectral sensitizer, it is advantageous to increase this part of the emulsion in sensitivity at wavelengths <480 nm by adding a suitable sensitizing dye. For example, dyes of the following formulas are suitable for this purpose:
Figure imgb0012
wherein
P
the links required to supplement a benzo-fused heterocyclic five-membered ring
R, T
O, S, N-R₇
R₉, R₁₀
CH₃, CH₃O, halogen and - if R or TO is - phenyl
and
Q, W₁, W₂, n, m
have the meaning given above.

Besonders geeignet sind beispielsweise folgende Farbstoffe:

Figure imgb0013
Figure imgb0014
Figure imgb0015
Wesentlicher Bestandteil der wenigstens einen lichtempfindlichen Schicht neben dem Silberhalogenid ist das Bindemittel.The following dyes are particularly suitable, for example:
Figure imgb0013
Figure imgb0014
Figure imgb0015
The binder is an essential component of the at least one light-sensitive layer in addition to the silver halide.

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-vinylpyrolidon, 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-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 generally 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.

Die Bindemittel sollen über eine ausreichende Menge an funktionellen Gruppen verfügen, so daß durch Umsetzung mit geeigneten Härtungsmitteln genügend widerstandsfähigen 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 by reaction enough suitable layers can be produced 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 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 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.

Bei dem als lichtempfindlichen Bestandteil in dem fotografischen Material befindlichen 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 größer als 5:1 ist, wobei der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einem Kreisinhalt entsprechend der projizierten Fläche des Kornes.The silver halide present as a light-sensitive component in the photographic material can be predominantly compact crystals, which are e.g. are regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals may preferably also be present, the average ratio of diameter to thickness of which is preferably greater than 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.

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 Korngrößenverteilung kann sowohl homo- als auch heterodispers sein. Homodisperse Korngrößenverteilung bedeutet, daß 95 % der Körner nicht mehr als ± 30% von der mittleren Korngröße abweichen. 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 doping of the individual grain areas, being different. The grain size distribution can be both homodisperse and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. In addition to the silver halide, the emulsions can also contain organic silver salts, for example 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 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.

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 Silberionenüberschluß möglich. Außer durch Fällung können die Silberhalogenidkristalle auch durch physikalische Reifung (Ostwaldreifung), in Gegenwart von überschüssigem Halogenid und/oder Silberhalogenidkomplexierungsmittel wachsen. 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, 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 merge The water-soluble silver salts and the halides are optionally carried out 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 an excess of halide, so-called inverse precipitation with an excess of 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, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.

Die fotografischen Emulsionen können zusätzlich zu den erfindungsgemäß einzusetzenden mercaptosubstituierten Heterocyclen Verbindungen zur Verhinderung der Schleierbildung oder zur Stabilisierung der fotografischen Funktion während der Produktion, der Lagerung oder der fotografischen Verarbeitung enthalten, insbesondere auch in der im Bereich von 480 bis 580 nm empfindlichen Schicht.In addition to the mercapto-substituted heterocycles to be used according to the invention, the photographic emulsions can contain compounds for preventing the formation of fog or for stabilizing the photographic function during production, storage or photographic processing, in particular also in the layer which is sensitive in the range from 480 to 580 nm.

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, Mercaptothiadiazole, 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 for example from 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, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example 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 be surface-active Contain 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 (e.g. acceleration of development, high contrast, sensitization, etc.).

Die chemische Sensibilisierung kann durch labile Schwefelverbindungen (z.B. Thiosulfat, Diacetyl-thioharnstoff), durch Gold-Schwefelreifung oder Reduktionsreifung erfolgen. Die chemische Sensibilisierung kann unter Zusatz von Ir, Rh, Pb, Cd, Hg, Au erfolgen, ebenso ist Zusatz von optischen Sensibilisatoren oder Stabilisatoren möglich.Chemical sensitization can take place through unstable sulfur compounds (e.g. thiosulfate, diacetyl-thiourea), through gold-sulfur ripening or reduction ripening. Chemical sensitization can be carried out with the addition of Ir, Rh, Pb, Cd, Hg, Au, as well as the addition of optical sensitizers or stabilizers.

Das fotografische Material kann weiterhin UV-Licht absorbierende Verbindungen, Weißtöner, Abstandshalter, Formalinfänger und anderes enthalten.The photographic material may further contain UV light absorbing compounds, whites, spacers, 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-A3 314 794 und 3 352 681), Benzophenonverbindungen (JP-A 2784/71), Zimtsäureesterverbindungen (US-A 3 705 805 und 3 707 375), Butadienverbindungen (US-A 4 045 229) 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 Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. Nos. A3,314,794 and 3,352,681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US Pat. No. 3,705,805) and 3,707,375), butadiene compounds (US-A 4,045,229) or benzoxazole compounds (US-A 3,700,455).

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

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

Der mittlere Teilchendurchmesser der Abstandshalter leigt insbesondere im Bereich von 0,2 bis 10 µm. 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 Ethylenimintyps, 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 ethyleneimine type, the acryloyl type or the vinylsulfone type. Diazine, triazine or 1,2-dihydroquinoline series hardeners 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 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).

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 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.

Geeignete Beispiele für Soforthärter sind z.B. Verbindungen der allgemeinen Formeln

Figure imgb0016

worin

R₁
Alkyl, Aryl oder Aralkyl bedeutet,
R₂
die gleiche Bedeutung wie R₁ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel
Figure imgb0017
 verknüpft ist, oder
R₁ und R₂
zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
R₃
für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR₄-COR₅, -(CH₂)m-NR₈R₉, -(CH₂)n-CONR₁₃R₁₄ oder
Figure imgb0018
 oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei
R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, und R₁₉
Wasserstoff oder C₁-C₄-Alkyl,
R₅
Wasserstoff, C₁-C₄-Alkyl oder NR₆R₇,
R₈
- COR₁₀
R₁₀
NR₁₁R₁₂
R₁₁
C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
R₁₂
Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
R₁₃
Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
R₁₆
Wasserstoff, C₁-C₄-Alkyl, COR₁₈ oder CONHR₁₉,
m
eine Zahl 1 bis 3
n
eine Zahl 0 bis 3
p
eine Zahl 2 bis 3 und
Y
O oder NR₁₇ bedeuten oder
R₁₃ und R₁₄
gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
Z
die zur Vervollständigung eines 5- oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und
X⊖
ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;
Figure imgb0019
   worin
R₁, R₂, R₃ und X⊖
die für Formel (a) angegebene Bedeutung besitzen.
Suitable examples of instant hardeners are, for example, compounds of the general formulas
Figure imgb0016
wherein
R₁
Means alkyl, aryl or aralkyl,
R₂
has the same meaning as R₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula
Figure imgb0017
 is linked, or
R₁ and R₂
together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C₁-C₃alkyl or halogen,
R₃
for hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, - (CH₂) m -NR₈R₉, - (CH₂) n -CONR₁₃R₁₄ or
Figure imgb0018
 or a bridge link or a direct bond to a polymer chain, wherein
R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉
Hydrogen or C₁-C₄ alkyl,
R₅
Hydrogen, C₁-C₄-alkyl or NR₆R₇,
R₈
- COR₁₀
R₁₀
NR₁₁R₁₂
R₁₁
C₁-C₄ alkyl or aryl, especially phenyl,
R₁₂
Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₃
Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₆
Hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,
m
a number 1 to 3
n
a number 0 to 3
p
a number 2 to 3 and
Y
O or NR₁₇ mean or
R₁₃ and R₁₄
together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, for example, by C₁-C₃alkyl or halogen,
Z.
the carbon atoms required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring, and
X ⊖
mean an anion which is omitted if an anionic group is already linked to the rest of the molecule;
Figure imgb0019
wherein
R₁, R₂, R₃ and X ⊖
have the meaning given for formula (a).

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

Beispiel 1 (Vergleichsversuch) Example 1

Eine durch teilweise Konvertierung hergestellte AgClBrI-Emulsion mit 40 % AgCl, 59,5 % AgBr und 0,5 % AgI, dotiert mit 4·10⁻⁸ Mol NaRhCl₄/Mol AgNO₃ und 2·10⁻⁵ Mol Na₂IrCl₆/Mol AgNo₃, mittl. Korndurchmesser 0,42 µm, wird auf bekannte Weise entsalzt und nach Zusatz von 20 µm Thiosulfat/Mol AgNo₃ unter sensitometrischer Kontrolle zu einem optimalen Empfindlichkeits-Schleier-Verhältnis gereift. Die Emulsion enthält 100 g AgNO₃ in 1 kg Emulsion.An AgClBrI emulsion produced by partial conversion with 40% AgCl, 59.5% AgBr and 0.5% AgI, doped with 4 · 10⁻⁸ mol NaRhCl₄ / mol AgNO₃ and 2 · 10⁻⁵ mol Na₂IrCl₆ / mol AgNo₃, mean . Grain diameter 0.42 microns, is desalted in a known manner and matured after the addition of 20 microns thiosulfate / mole AgNo₃ under sensitometric control to an optimal sensitivity-fog ratio. The emulsion contains 100 g of AgNO₃ in 1 kg of emulsion.

Grünsensibilisierte Teilemulsion: 300 g der Emulsion werden durch Zusatz von 37 mg des Sensibilisators SE 18 für den grünen Spektalbereich optisch sensibilisiert und durch Zusatz von 30 mg 5-Hydroxy-7-methyl-1,3,8-triazaindolizin pro kg Emulsion stabilisiert.Green-sensitized partial emulsion: 300 g of the emulsion are optically sensitized for the green spectral range by adding 37 mg of the sensitizer SE 18 and stabilized by adding 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine per kg of emulsion.

Unsensibilisierte Teilemulsion: 700 g der Emulsion werden durch Zusatz von 30 mg 5-Hydroxy-7-methyl-1,3,8-triazaindolizin stabilisiert. Die Teilemulsionen werden vermischt; ein Teil wird unter Zusatz eines Gelatinehärtungsmittels auf einem opaken Träger vergossen (Versuch 1A). Ein anderer Teil der Mischung wird 4 Stunden bei 40° C gehalten und dann unter Zusatz eines Gelatinehärtungsmittels vergossen (Versuch 1B).Unsensitized partial emulsion: 700 g of the emulsion are stabilized by adding 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine. The partial emulsions are mixed; a part is cast on an opaque support with the addition of a gelatin hardening agent (test 1A). Another part of the mixture is kept at 40 ° C. for 4 hours and then poured with the addition of a gelatin hardening agent (experiment 1B).

Beispiel 2 (erfindungsgemäß) Example 2

Emulsionsherstellung und Sensibilisierung für den Spektralbereich von 480 bis 580 nm erfolgt gemäß Beispiel 1.Emulsion preparation and sensitization for the spectral range from 480 to 580 nm is carried out according to Example 1.

Unsensibilisierte Teilemulsion: Dieser Teil der Emulsion wird wie in Beispiel 1 mit 30 mg 5-Hydroxy-7-methyl-1,3,8-triazaindolizin und zusätzlich mit 200 mg Stabilisator III pro kg Emulsion stabilisiert.Unsensitized partial emulsion: This part of the emulsion is stabilized as in Example 1 with 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine and additionally with 200 mg of Stabilizer III per kg of emulsion.

Die Teilemulsionen werden gemäß Beispiel 1 vermischt und vergossen (Versuche 2A und 2B).The partial emulsions are mixed and poured according to Example 1 (tests 2A and 2B).

Beispiel 3 (erfindungsgemäß) Example 3

Emulsionsherstellung und Sensibilisierung für den Spektralbereich von 480 bis 580 nm entsprechen Beispiel 1, allerdings werden 250 g einer Emulsion aus 60 Mol-% AgCl, 39,5 Mol-% AgBr und 0,5 Mol-% AgI verwendet.Emulsion preparation and sensitization for the spectral range from 480 to 580 nm correspond to Example 1, but 250 g of an emulsion of 60 mol% AgCl, 39.5 mol% AgBr and 0.5 mol% AgI are used.

Blausensibilisierte Teilemulsion: 250 g der unsensibilisierten Emulsion werden mit 20 mg Sensibilisator BS6 und 30 mg 5-Hydroxy-7-methyl-1,3,8-triazaindolizin versetzt.Blue-sensitized partial emulsion: 250 mg of the unsensitized emulsion are mixed with 20 mg of sensitizer BS6 and 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine.

Unsensibilisierte Teilemulsion: 500 g der unsensibilisierten Emulsion werden mit 30 mg 5-Hydroxy-7-methyl-1,3,8-triazaindolizin und 160 mg Stabilisator I versetzt.Unsensitized partial emulsion: 500 g of the unsensitized emulsion are mixed with 30 mg of 5-hydroxy-7-methyl-1,3,8-triazaindolizine and 160 mg of stabilizer I.

Die drei Teilemulsionen werden gemischt und gemäß Beispiel vergossen (Versuche 3A und 3B).The three partial emulsions are mixed and cast according to the example (experiments 3A and 3B).

Fotografische Auswertung der Beispiele 1-3Photographic evaluation of examples 1-3

Eine Probe des Materials wird hinter einem Gelbfilter und einem Stufenteil belichtet. Eine 2. Probe wird hinter einem Purpurfilter und einem Stufenteil belichtet. Danach wird mit einem für SW-Papier üblichen Entwickler (z.B. Agfa 100) entwickelt und die Dichte der Stufen gemessen. Aus der Schwärzungskurve wird log ER nach ANSI-Norm PH 2.2-1966 bestimmt (Tabelle 1).A sample of the material is exposed behind a yellow filter and a step part. A second sample is exposed behind a purple filter and a step part. The developer is then developed with a developer customary for SW paper (e.g. Agfa 100) and the density of the steps is measured. Log ER is determined from the density curve in accordance with ANSI standard PH 2.2-1966 (Table 1).

(Bei Belichtung durch Gelbfilter erhält man eine Abbildung mit geringem Kontrast ≙ hohem log ER, durch Purpurfilter mit hohem Kontrast ≙ niedrigem log ER).(When exposed through a yellow filter, an image with a low contrast ≙ high log ER is obtained, with a purple filter with high contrast ≙ low log ER).

Künstliche AlterungArtificial aging

Ein Teil des Materials (1A, 2A, 3A) wird einer künstlichen Alterung unterworfen durch 2-tägige Lagerung in einer feuchtwarmen Atmosphäre bei 45°C und 65% rel. Feuchte (1C, 2C, 3C).Part of the material (1A, 2A, 3A) is subjected to an artificial aging by storage for 2 days in a warm, humid atmosphere at 45 ° C. and 65% rel. Humidity (1C, 2C, 3C).

Anschließend fotografische Auswertung wie beschrieben (Tabelle 2).

Figure imgb0020
Then photographic evaluation as described (Table 2).
Figure imgb0020

Beispiel 4Example 4

Analog zu Beispiel 1 werden die folgenden Emulsionen der angegebenen Zusammensetzung und Korngröße hergestellt und chemisch gereift. Jede Emulsion wird in 2 gleiche Teile geteilt, wovon die erste Teilemulsion mit dem Spektralsensibilisator im Bereich zwischen 480 und 580 nm sensibilisiert wird und die zweite Teilemulsion erfindungsgemäß mit dem Stabilisator versetzt wird. Dann weden die beiden Teilemulsionen vermischt und wie übliche auf PE-Papierunterlage mit einem Auftrag von 1,4 g Silber pro m² vergossen. Diese erfindungsgemäßen Proben erhalten die Bezeichnung A.Analogously to Example 1, the following emulsions of the specified composition and grain size are prepared and chemically ripened. Each emulsion is divided into 2 equal parts, of which the first partial emulsion is sensitized with the spectral sensitizer in the range between 480 and 580 nm and the second partial emulsion is mixed with the stabilizer according to the invention. Then the two partial emulsions are mixed and cast as usual on PE paper base with an application of 1.4 g of silver per m². These samples according to the invention are designated A.

Zum Vergleich werden 2 weitere Proben B und C hergestellt: Die Proben B unterscheiden sich von A durch Weglassen des Stabilisators in der zweiten Teilemulsion. Die Proben C enthalten den Spektralsensibilisator gleichmäßig verteilt auf alle Emulsionskristalle in der gleichen Konzentration pro m² wie bei den Proben A und B.For comparison, 2 further samples B and C are produced: Samples B differ from A in that the stabilizer in the second partial emulsion is omitted. Samples C contain the spectral sensitizer evenly distributed over all emulsion crystals in the same concentration per m² as for samples A and B.

Die Proben werden dann einer sensitometrischen Belichtung unterworfen hinter einem Gelb- und einem Purpurfilter mit der im Fig. 1 angegebenen Spektralcharakteristik "Gb" bzw. "Pp". Anschließend wird in Agfa-Neutol-Papierentwickler entwickelt und log ER bestimmt.The samples are then subjected to sensitometric exposure behind a yellow and a purple filter with the spectral characteristics "Gb" and "Pp" shown in FIG. 1. It is then developed in Agfa-Neutol paper developer and log ER determined.

Die Ergebnisse sind in den Tabelle 3-5 angegeben. Die Tabellen 3-5 enthalten in

Spalte 1
die Art der Probe (A, B oder C),
Spalte 2
den verwendeten Sensibilisator
Spalte 3
die Sensibilisatormenge in µ Mol pro Mol Silber der ersten Teilemulsion bzw. der gesamten Emulsion bei den Proben C
Spalte 4
den verwendeten Stabilisator
Spalte 5
die Menge des Stabilisators in mg pro Mol Silber der zweiten Teilemulsion
Spalte 6
log ER hinter Gb-Filter
Spalte 7
log ER hinter Pp-Filter
Spalte 8
das spektrale Sensibilisierungsmaximum in nm
Tabelle 3 Emulsion: 85 % Br⊖, 15 % Cl⊖, Korngröße: 0,34 µm 1 2 3 4 5 6 7 8 A SE5 200 VIII 300 1,12 0,67 540 B SE5 200 - - 0,75 0,68 540 C SE5 100 - - 0,64 0,66 540 A SE3 200 IX 300 1,15 0,71 520 B SE3 200 - - 0,85 0,75 520 C SE3 100 - - 0,71 0,73 520 A SE16 200 I 300 1,12 0,69 525 B SE16 200 - - 0,75 0,74 525 C SE16 100 - - 0,73 0,72 525 A SE17 200 III 300 1,28 0,79 545 B SE17 200 - - 0,78 0,72 545 C SE17 100 - - 0,65 0,70 545 A SE1 50 III 400 1,13 0,68 545 B SE1 50 - - 0,86 0,74 545 C SE1 25 - - 0,72 0,64 545 A SE18 50 XII 400 1,16 0,67 545 B SE18 50 - - 0,78 0,72 545 C SE18 25 - - 0,74 0,73 545 A SE18 50 XII 200 1,22 0,75 545 A SE1 50 III 200 1,17 0,72 545 Tabelle 4 Emulsion: 85 % Br⊖, 15 % Cl⊖, Korngröße: 0,34 µm 1 2 3 4 5 6 7 8 A SE12 50 III 300 1,05 0,75 535 B SE12 50 - - 0,70 0,79 535 C SE12 25 - - 0,69 0,78 535 A SE13 50 XII 300 0,98 0,76 530 B SE13 50 - - 0,58 0,69 530 C SE13 25 - - 0,62 0,67 530 A SE14 50 XIII 300 1,10 0,75 515 B SE14 50 - - 0,71 0,71 515 C SE14 25 - - 0,62 0,72 515 A SE15 50 III 300 0,99 0,75 530 B SE15 50 - - 0,61 0,72 530 C SE15 25 - - 0,63 0,73 530 A SE8 200 XI 150 1,19 0,70 530 B SE8 200 - - 0,89 0,69 530 C SE8 100 - - 0,78 0,67 530 A SE4 200 XIII 150 1,05 0,68 520 B SE4 200 - - 0,72 0,65 520 C SE4 100 - - 0,70 0,65 520 A SE6 200 XI 200 1,36 0,65 545 B SE6 200 - - 0,90 0,68 545 C SE6 100 - - 0,85 0,67 545 Tabelle 5 Emulsion: 60 % Br⊖, 40 % Cl⊖, Korngröße: 0,42 µm 1 2 3 4 5 6 7 8 A SE10 200 XIII 300 1,12 0,62 515 B SE10 200 - - 0,91 0,64 515 C SE10 100 - - 0,70 0,65 515 A SE9 150 VII 300 0,95 0,71 510 B SE9 150 - - 0,83 0,70 510 C SE9 75 - - 0,80 0,71 510 A SE2 200 VI 150 1,19 0,66 550 B SE2 200 - - 0,82 0,66 550 C SE2 100 - - 0,73 0,62 550 A SE7 200 II 150 1,05 0,69 525 B SE7 200 - - 0,85 0,73 525 C SE7 100 - - 0,80 0,68 525 A SE2 50 IX 200 1,13 0,75 550 B SE2 50 - - 0,87 0,73 550 C SE2 25 - - 0,81 0,74 550 A SE1 100 III 200 1,16 0,71 550 B SE1 100 - - 0,95 0,68 550 C SE1 50 - - 0,75 0,63 550 A SE18 100 XII 200 1,30 0,64 550 B SE18 100 - - 1,10 0,68 550 C SE18 50 - - 0,67 0,65 550 The results are shown in Table 3-5. Tables 3-5 contain in
Column 1
the type of sample (A, B or C),
Column 2
the sensitizer used
Column 3
the amount of sensitizer in moles per mole of silver of the first partial emulsion or of the entire emulsion in samples C.
Column 4
the stabilizer used
Column 5
the amount of stabilizer in mg per mole of silver of the second partial emulsion
Column 6
ER log behind Gb filter
Column 7
ER log behind PP filter
Column 8
the spectral sensitization maximum in nm
Table 3 Emulsion: 85% Br ⊖ , 15% Cl ⊖ , grain size: 0.34 µm 1 2nd 3rd 4th 5 6 7 8th A SE5 200 VIII 300 1.12 0.67 540 B SE5 200 - - 0.75 0.68 540 C. SE5 100 - - 0.64 0.66 540 A SE3 200 IX 300 1.15 0.71 520 B SE3 200 - - 0.85 0.75 520 C. SE3 100 - - 0.71 0.73 520 A SE16 200 I. 300 1.12 0.69 525 B SE16 200 - - 0.75 0.74 525 C. SE16 100 - - 0.73 0.72 525 A SE17 200 III 300 1.28 0.79 545 B SE17 200 - - 0.78 0.72 545 C. SE17 100 - - 0.65 0.70 545 A SE1 50 III 400 1.13 0.68 545 B SE1 50 - - 0.86 0.74 545 C. SE1 25th - - 0.72 0.64 545 A SE18 50 XII 400 1.16 0.67 545 B SE18 50 - - 0.78 0.72 545 C. SE18 25th - - 0.74 0.73 545 A SE18 50 XII 200 1.22 0.75 545 A SE1 50 III 200 1.17 0.72 545 Emulsion: 85% Br ⊖ , 15% Cl ⊖ , grain size: 0.34 µm 1 2nd 3rd 4th 5 6 7 8th A SE12 50 III 300 1.05 0.75 535 B SE12 50 - - 0.70 0.79 535 C. SE12 25th - - 0.69 0.78 535 A SE13 50 XII 300 0.98 0.76 530 B SE13 50 - - 0.58 0.69 530 C. SE13 25th - - 0.62 0.67 530 A SE14 50 XIII 300 1.10 0.75 515 B SE14 50 - - 0.71 0.71 515 C. SE14 25th - - 0.62 0.72 515 A SE15 50 III 300 0.99 0.75 530 B SE15 50 - - 0.61 0.72 530 C. SE15 25th - - 0.63 0.73 530 A SE8 200 XI 150 1.19 0.70 530 B SE8 200 - - 0.89 0.69 530 C. SE8 100 - - 0.78 0.67 530 A SE4 200 XIII 150 1.05 0.68 520 B SE4 200 - - 0.72 0.65 520 C. SE4 100 - - 0.70 0.65 520 A SE6 200 XI 200 1.36 0.65 545 B SE6 200 - - 0.90 0.68 545 C. SE6 100 - - 0.85 0.67 545 Emulsion: 60% Br ⊖ , 40% Cl ⊖ , grain size: 0.42 µm 1 2nd 3rd 4th 5 6 7 8th A SE10 200 XIII 300 1.12 0.62 515 B SE10 200 - - 0.91 0.64 515 C. SE10 100 - - 0.70 0.65 515 A SE9 150 VII 300 0.95 0.71 510 B SE9 150 - - 0.83 0.70 510 C. SE9 75 - - 0.80 0.71 510 A SE2 200 VI 150 1.19 0.66 550 B SE2 200 - - 0.82 0.66 550 C. SE2 100 - - 0.73 0.62 550 A SE7 200 II 150 1.05 0.69 525 B SE7 200 - - 0.85 0.73 525 C. SE7 100 - - 0.80 0.68 525 A SE2 50 IX 200 1.13 0.75 550 B SE2 50 - - 0.87 0.73 550 C. SE2 25th - - 0.81 0.74 550 A SE1 100 III 200 1.16 0.71 550 B SE1 100 - - 0.95 0.68 550 C. SE1 50 - - 0.75 0.63 550 A SE18 100 XII 200 1.30 0.64 550 B SE18 100 - - 1.10 0.68 550 C. SE18 50 - - 0.67 0.65 550

Wie man den erfindungsgemäßen Proben A der Tabellen 3-5 entnimmt, ist die Gamma-Differenzierung bei Belichtung hinter dem Gelbfilter (Spalte 6) wesentlich höher als bei den stabilisatorfreien Vergleichsproben B und C.As can be seen from samples A according to the invention in Tables 3-5, the gamma differentiation when exposed behind the yellow filter (column 6) is significantly higher than with the stabilizer-free comparison samples B and C.

Beispiel 5Example 5

Eine Silberchlorid-Emulsion mit 70 Mol-% Chlorid und 30 Mol-% Bromid sowie einer mittleren Korngröße von 0,3 µ wird hergestellt und chemisch gereift wie im Beispiel 1 beschrieben.A silver chloride emulsion with 70 mol% chloride and 30 mol% bromide and an average grain size of 0.3 μ is produced and chemically ripened as described in Example 1.

Die Emulsion wird dann, wie in Beispiel 4 beschrieben in zwei gleiche Teile geteilt. Die erste Teilemulsion wird mit 75 µMol pro Mol Ag des Sensibilisatorfarbstoffs SE 6 sensibilisiert. Die zweite Teilemulsion wird mit einem Blausensibilisator BS wie in Tabelle 6 angegeben sensibilisiert und mit 240 mg des Stabilisators III stabilisiert. Nach Vermischen der Teilemulsionen wird auf PE-Papierunterlagen vergossen. Die Schichten werden wie in Beispiel 4 einer sensitometrischen Belichtung hinter Gelb- und Purpurfilter unterworfen.The emulsion is then divided into two equal parts as described in Example 4. The first partial emulsion is sensitized with 75 μmol per mole Ag of the sensitizer dye SE 6. The second partial emulsion is sensitized with a blue sensitizer BS as indicated in Table 6 and stabilized with 240 mg of stabilizer III. After the part emulsions have been mixed, they are poured onto PE paper substrates. As in Example 4, the layers are subjected to sensitometric exposure behind a yellow and purple filter.

Die Ergebnisse enthält Tabelle 6.The results are shown in Table 6.

Die Tabelle 6 enthält in

Spalte 1
den Blausensibilisator BS
Spalte 2
die Menge des Blausensibilisators in µMol pro Mol Ag der zweiten Teilemulsion
Spalte 3
log ER hinter Gb-Filter
Spalte 4
log ER hinter Pp-Filter
Spalte 5
die Zunahme der Empfindlichkeit hinter Pp-Filter in relativen log-Einheiten im Vergleich zu einer BS-freien Probe
Spalte 6 uns 7
die spektralen Sensibilisierungsmaxima in nm
Tabelle 6 Emulsion: 70 % Cl⊖, 30 % Br⊖, 0,30 µm 1 2 3 4 5 6 7 BS8 20 1,07 0,50 0,35 467 545 BS4 40 1,01 0,53 0,40 470 545 BS6 40 1,20 0,51 0,25 455 545 BS3 40 1,16 0,55 0,15 445 545 BS7 40 1,10 0,51 0,30 470 545 - - 1,18 0,52 - - 545 Table 6 contains in
Column 1
the blue sensitizer BS
Column 2
the amount of the blue sensitizer in µmoles per mole Ag of the second partial emulsion
Column 3
ER log behind Gb filter
Column 4
ER log behind PP filter
Column 5
the increase in sensitivity behind Pp filters in relative log units compared to a BS-free sample
Column 6 and 7
the spectral sensitization maxima in nm
Table 6 Emulsion: 70% Cl ⊖ , 30% Br ⊖ , 0.30 µm 1 2nd 3rd 4th 5 6 7 BS8 20th 1.07 0.50 0.35 467 545 BS4 40 1.01 0.53 0.40 470 545 BS6 40 1.20 0.51 0.25 455 545 BS3 40 1.16 0.55 0.15 445 545 BS7 40 1.10 0.51 0.30 470 545 - - 1.18 0.52 - - 545

Wie man der Tabelle 6 entnimmt läßt sich die Blauempfindlichkeit (Spalte 5) durch Zusatz der Blausensibilisatoren erheblich steigern ohne Verlust der erfindungsgemäßen Gamma-Differenzierung.As can be seen from Table 6, the blue sensitivity (column 5) can be increased considerably by adding the blue sensitizers without losing the gamma differentiation according to the invention.

Claims (5)

  1. A gradation-variable BW paper comprising at least one silver halide emulsion layer of a mixture of at least two photosensitive silver halide emulsions, of which one has its absorption maximum in the range from 480 to 580 nm while the other has its absorption maximum below 480 nm, characterized in that the emulsion which has its absorption maximum below 480 nm contains a compound corresponding to the following formula:
    Figure imgb0023
     in which
    X   represents the remaining members of an optionally benzo- or naphtho-condensed heterocycle optionally containing further substituents.
  2. A gradation-variable BW paper as claimed in claim 1, characterized in that the emulsion which has its absorption maximum below 480 nm contains a compound corresponding to the following formula:
    Figure imgb0024
     in which
    R₁ and R₂ are the remaining members of a benzo or naphtho radical substituted by at least one sulfo group and optionally containing further substituents.
  3. A gradation-variable BW paper as claimed in claim 2, in which R₁ and R₂ represent the remaining members of a benzo or naphtho radical substituted by one or two sulfo groups and optionally substituted by C₁₋₄ alkyl or halogen.
  4. A gradation-variable BW paper as claimed in claim 1, characterized in that the emulsions contain silver halides of 20 to 80 mol-% chloride, 20 to 80 mol-% bromide and 0 to 5 mol-% iodide.
  5. A gradation-variable BW paper as claimed in claim 1, characterized in that the average grain size of the silver halide emulsions is from 0.2 to 0.6 µm.
EP88119074A 1987-11-24 1988-11-17 Gradation-variable black and white paper Expired - Lifetime EP0317886B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873739766 DE3739766A1 (en) 1987-11-24 1987-11-24 GRADATION VARIABLE SW PAPER
DE3739766 1987-11-24

Publications (3)

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EP0317886A2 EP0317886A2 (en) 1989-05-31
EP0317886A3 EP0317886A3 (en) 1990-12-27
EP0317886B1 true EP0317886B1 (en) 1994-03-16

Family

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Family Applications (1)

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EP (1) EP0317886B1 (en)
JP (1) JP2622407B2 (en)
DE (2) DE3739766A1 (en)
ES (1) ES2050139T3 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0373339B1 (en) * 1988-11-15 1994-05-04 Agfa-Gevaert AG Silver halide recording material
DE58907695D1 (en) * 1989-01-07 1994-06-23 Agfa Gevaert Ag Silver halide recording material.
JPH046550A (en) * 1990-04-24 1992-01-10 Mitsubishi Paper Mills Ltd Silver halide photographic material
JP2597431B2 (en) * 1991-04-24 1997-04-09 三菱製紙株式会社 Silver halide photographic material
DE69224837T2 (en) * 1992-10-30 1998-10-08 Agfa Gevaert Nv Photographic material containing a mixture of silver halide emulsions
DE69327635T2 (en) * 1992-11-19 2000-08-10 Eastman Kodak Co., Rochester Dye compounds and photographic elements containing them
DE69329964T2 (en) * 1992-11-19 2001-09-13 Eastman Kodak Co., Rochester Furan or pyrrole substituted dye compounds and photographic silver halide elements containing such dyes
JP3588160B2 (en) * 1994-05-18 2004-11-10 イーストマン コダック カンパニー Blue sensitizing dye having heterocyclic substituent
JPH07325361A (en) * 1994-06-02 1995-12-12 Mitsubishi Paper Mills Ltd Silver halide photographic sensitive material
DE19601141C2 (en) * 1995-07-31 1998-08-20 Agfa Gevaert Ag Gradation-variable black and white paper
GB9626281D0 (en) * 1996-12-18 1997-02-05 Kodak Ltd Photographic high contrast silver halide material

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Publication number Priority date Publication date Assignee Title
CA539568A (en) * 1957-04-16 D. Hill George Prevention of dye wandering in photographic emulsions
GB494088A (en) * 1937-03-18 1938-10-18 Frank Forster Renwick Improvements in or relating to photographic printing processes and materials
GB561875A (en) * 1942-12-03 1944-06-08 John David Kendall Improvements in or relating to photographic materials
FR1222449A (en) * 1958-07-31 1960-06-09 Kodak Pathe New photographic silver halide emulsion
BE595325A (en) * 1960-09-23
BE629343A (en) * 1962-03-08
GB1225241A (en) * 1967-04-21 1971-03-17
GB1298302A (en) * 1971-04-05 1972-11-29 Agfa Gevaert Ag Process for the photographic production of equidensities
DE3020163A1 (en) * 1980-05-28 1981-12-03 Agfa-Gevaert Ag, 5090 Leverkusen PHOTOGRAPHIC RECORDING MATERIAL AND THE USE THEREOF FOR PRODUCING IMAGES
DE3028167A1 (en) * 1980-07-25 1982-04-01 Agfa-Gevaert Ag, 5090 Leverkusen Variable contrast photographic printing paper - has two layer emulsion with different colour gradations
DE3635388A1 (en) * 1985-10-22 1987-04-23 Konishiroku Photo Ind LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL
DE3605713A1 (en) * 1986-02-22 1987-08-27 Agfa Gevaert Ag COLOR PHOTOGRAPHIC RECORDING MATERIAL

Also Published As

Publication number Publication date
DE3739766A1 (en) 1989-06-08
US5006455A (en) 1991-04-09
JPH01167745A (en) 1989-07-03
ES2050139T3 (en) 1994-05-16
JP2622407B2 (en) 1997-06-18
EP0317886A2 (en) 1989-05-31
DE3888461D1 (en) 1994-04-21
EP0317886A3 (en) 1990-12-27

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