EP0141128B1 - Colour-photographic recording material - Google Patents

Colour-photographic recording material Download PDF

Info

Publication number
EP0141128B1
EP0141128B1 EP84110240A EP84110240A EP0141128B1 EP 0141128 B1 EP0141128 B1 EP 0141128B1 EP 84110240 A EP84110240 A EP 84110240A EP 84110240 A EP84110240 A EP 84110240A EP 0141128 B1 EP0141128 B1 EP 0141128B1
Authority
EP
European Patent Office
Prior art keywords
layer
silver
material according
mol
sensitive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84110240A
Other languages
German (de)
French (fr)
Other versions
EP0141128A2 (en
EP0141128A3 (en
Inventor
Helmut Dr. Kampfer
Hans Dr. Langen
Erwin Dr. Ranz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0141128A2 publication Critical patent/EP0141128A2/en
Publication of EP0141128A3 publication Critical patent/EP0141128A3/en
Application granted granted Critical
Publication of EP0141128B1 publication Critical patent/EP0141128B1/en
Expired legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/3924—Heterocyclic

Definitions

  • the invention relates to a color photographic recording material with improved fog resistance, which has at least one light-sensitive silver halide emulsion layer and at least one layer which contains colloidal silver.
  • Photographic materials undergo a number of adverse changes during storage, including the loss of sensitivity and the increase in fog. These deficiencies occur particularly easily if the material contains layers that contain colloidal silver as a light-absorbing medium. Such layers are arranged, for example, as a silver filter yellow layer (according to Carey Lea) for absorbing unwanted blue light between the blue-sensitive and the green- and red-sensitive layers.
  • a gray, black or blue colloidal silver-containing antihalation layer can be applied under the light-sensitive layers in order to prevent the backscattering of light into the light-sensitive layers and thus a deterioration in sharpness.
  • the advantage of silver as a light-absorbing medium over organic dyes for filter layers is usually that the same absorption effect can be achieved with much thinner layers.
  • a layer containing colloidal silver can adversely affect the photographic properties of the adjacent light-sensitive partial layers. This can be particularly noticeable during storage due to increased fog and loss of sensitivity.
  • Antifoggants which can be used are above all heterocyclic compounds, such as benzimidazoles, benzotriazoles and heterocyclic mercapto compounds, in particular 1-phenyl-5-mercaptotetrazole and its 1-amidophenyl and 1-ureidophenyl derivatives. According to DE-OS 1 547 694 and US Pat. No.
  • No. 3,695,881 discloses a method for producing images in which iodide ions from an emulsion containing silver iodide increases the solubility of another emulsion which has been treated with a phenyl mercaptotetrazole. According to DE-OS 2 437 353 and GB 1 471 554, contamination by silver in the development of black and white materials should be avoided by development in the presence of amidophenyl mercaptotetrazoles.
  • antifoggants with excellent activity are among the proposed compounds, particularly mercaptotetrazole derivatives, they generally have the serious disadvantage that they reduce the photographic sensitivity to a greater or lesser extent by hindering the bleaching of the developed silver during processing or that they contribute to adverse changes in the photographic properties by diffusion into light-sensitive neighboring layers.
  • the object of the invention is to provide an improved color photographic material with at least one light-sensitive silver halide emulsion layer and at least one layer containing colloidal silver, which does not have these disadvantages, in particular the reduction in photographic sensitivity, to the known extent.
  • the antifoggants correspond to the following formula la in which the substituents have the meaning given above.
  • Suitable substituents for R 1 , R 2 , Ar and Het are those which are suitable for antifoggants in light-sensitive silver halide materials, for example hydroxyl, alkoxy, such as, for example, methoxy or ethoxy, halogen, such as fluorine, chlorine or bromine. Het in particular can also be substituted with an aryl, preferably with a phenyl radical.
  • R 1 is hydrogen or an alkyl radical.
  • R 2 represents an alkyl radical.
  • M preferably represents hydrogen.
  • the recording material has at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive layer.
  • the colloidal silver-containing layer is a yellow filter layer, the silver-free layer being arranged with a connection I between the yellow filter layer and a green- or red-sensitive layer.
  • the material according to the invention each has at least one blue, green and red sensitive layer and an antihalation layer with colloidal silver, a silver-free layer with the compound 1 to be used according to the invention being arranged between the antihalation layer and the specified layers.
  • the present invention compounds to be used are preferably used in amounts of from 10- 2 to 10- 8 mol / m 2, preferably in amounts of from 10- 4 to 10- 6 mol / m 2 of the silver-free layers added.
  • colored photographic images can be produced by a wide variety of processes, e.g. according to the silver color bleaching process or according to the color diffusion process.
  • the material according to the invention is particularly suitable for producing colored photographic images by chromogenic development in the presence of color couplers which react with the oxidation product of developers, generally p-phenylenediamines, to form dyes.
  • the color couplers can be added to the color developer.
  • the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers.
  • the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or a-naphthol type.
  • the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used.
  • the blue-sensitive layer can contain, for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • the color couplers can e.g. are 6-, 4- and 2-equivalent couplers, including the so-called white couplers, which do not produce any dye when reacted with color developer oxidation products, and DIR couplers.
  • Suitable couplers are known, for example, from the publications “Color Coupler” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff”, Volume 111, page 111 (1961), K. Venkataraman in “The Chemistry of Synthetic Dyes”, Vol. 4, 341 to 387, Academic Press (1971) and TH games, "The Theory of the Photographic Process", 4th Ed., pp. 353-362, and from Research Disclosure No. 17643 of December 1978, Section VII.
  • the color photographic recording materials according to the invention preferably contain at least one silver halide emulsion layer unit for recording light from each of the three spectral ranges red, green and blue.
  • Each of these layer units can comprise a single silver halide emulsion layer or also a plurality of silver halide emulsion layers.
  • Color photographic recording materials with double layers for the different spectral ranges are known, for example, from US Pat. Nos. 3,663,228, 3,849,138 and 4,184,876.
  • the silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide.
  • the halide content of at least one layer consists of 0 to 10 mol% of Agl, 0 to 10 mol% of AgCl and 0 to 100% of AgBr, the sum of these proportions being 100%.
  • the halide portion can also consist predominantly of chloride.
  • the silver halide horns can e.g. be cubic, octahedral or tabular.
  • the emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Chemical Engineering, 4th edition. Volume 18, pages 431 ff and on the above-mentioned Research Disclosure No. 17643, Section IV.
  • antifoggants In addition to the antifoggants to be used according to the invention, commonly used antifoggants and stabilizers can be used.
  • azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
  • Such connections are described, for example, in the article by Birr, Z. Wiss. Phot. 47, 1952), pp. 2-58.
  • Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17643 above in Section IV.
  • the usual layer supports can be used for the materials according to the invention, e.g. Cellulose ester supports, e.g. Cellulose acetate and polyester. Also suitable are paper supports, which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene.
  • Cellulose ester supports e.g. Cellulose acetate and polyester.
  • paper supports which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene.
  • polyolefins especially with polyethylene or polypropylene.
  • hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • Proteins in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • the layers can also contain other synthetic binders in dissolved or dispersed form, such as homo- or copolymers of acrylic or methacrylic acid or their derivatives, such as first, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
  • binders specified in Research Disclosure 17643 above in Section IX.
  • the layers of the photographic material can be hardened in the usual manner, for example with formaldehyde, with hardeners of the epoxy type, the heterocyclic ethyleneimine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German Offenlegungsschrift 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type.
  • Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl - N- ⁇ - (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N-ß-hydroxy-ethyl-aniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine.
  • the p-phenylenediamine type e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino
  • the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
  • the usual compounds can be used as bleaching agents, for example fur salts and Fe 3 + complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc.
  • Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, lminodiacetic acid, N-hydroxyethylethylenediamine diamine , Alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulphates are also suitable as bleaching agents.
  • the layers specified below are applied in succession to a cellulose triacetate support provided with an antihalation layer and an adhesive layer.
  • the stated quantities relate to 1 m 2 .
  • the silver application is indicated by specifying the equimolar amounts of silver nitrate:
  • the layer contains a silver bromide iodide emulsion (6 mol% silver iodide), a cyan coupler, a DIR coupler and a mask coupler. Silver application: 3.4 g.
  • the layer contains a silver bromide iodide emulsion with 10 mol% silver iodide and a cyan coupler. Silver application: 2.2 g.
  • the intermediate layer contains 0.7 g of gelatin, 0.09 g of a scavenger for developer oxidation products of the following formula dispersed therein:
  • the layer contains a silver bromide iodide emulsion (6 mol% silver iodide) as well as a purple coupler of the pyrazolone type, a DIR coupler and a yellow mask coupler.
  • the layer contains a silver bromide iodide emulsion (10 mol% silver iodide) and a purple coupler of the pyrazolone type dispersed therein.
  • the intermediate layer contains 0.5 g of gelatin and disperses therein the scavenger for developer oxidation products indicated under layer 3 and optionally the antifoggants indicated in Table 2 below.
  • the yellow filter layer contains colloidal silver. Density: 0.7.
  • the layer contains a silver bromide iodide emulsion (5 mol% silver iodide) and dispersed therein a mixture of yellow couplers of the benzoylacetanilide type.
  • the layer contains a blue-sensitive layer with 6 mol% of silver iodide and a mixture of the yellow couplers indicated under layer 8.
  • the layer contains 0.8 g of a benzotriazole-type UV absorber dispersed in gelatin.
  • the top layer consists of hardened gelatin.
  • the samples were subjected to the following storage conditions A to check their storage stability: 7 days storage at a temperature of 35% ° C, 90% relative humidity and with exclusion of light.
  • Example 1 According to the general construction scheme given in Example 1, five different assemblies to Q were produced, which differed in that the compounds listed in Table 3 below were added in the intermediate layer indicated under 6 between the yellow filter layer and the green-sensitive layer of high sensitivity.
  • Example 2 It can be seen from Example 2 that with increasing amount of the compounds to be used according to the invention, the increase in fog which occurs during storage A decreases.
  • Example 1 A recording material according to Example 1, Structure A is produced, but the compounds to be used according to the invention which are indicated in Table 4 below were introduced into the adhesive layer between the antihalation layer made of colloidal silver and the red-sensitive layer of low sensitivity.
  • the material is stored as described in Example 1 under storage conditions A and B, exposed and then developed as indicated in Example 1.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

Die Erfindung, betrifft ein farbfotografisches Aufzeichnungsmaterial mit verbesserter Schleierbeständigkeit, welches wenigstens eine lichtempfindliche Silberhalogenidemulsionsschicht und wenigstens eine Schicht, die kolloidales Silber enthält, aufweist.The invention relates to a color photographic recording material with improved fog resistance, which has at least one light-sensitive silver halide emulsion layer and at least one layer which contains colloidal silver.

Fotografische Materialien, insbesondere farbfotografische Mehrschichtenmaterialien, unterliegen während der Lagerung einer Reihe von nachteiligen Veränderungen, unter denen der Verlust an Empfindlichkeit und der Anstieg des Schleiers besonders ins Gewichtfallen. Diese Mängel treten besonders leicht auf, wenn im Material Schichten enthalten sind, die kolloidales Silber als lichtabsorbierendes Medium enthalten. Solche Schichten werden beispielsweise als Silberfiltergelbschicht (nach Carey Lea) zur Absorption unerwünschten blauen Lichtes zwischen dem blauempfindlichen und den grün- und rotempfindlichen Schichten angeordnet. Weiterhin kann unter die lichtempfindlichen Schichten eine graues, schwarzes oder blaues kolloidales Silber enthaltende Antihalationsschicht angebracht werden, um die Rückstreuung von Licht in die lichtempfindlichen Schichten und damit eine Schärfeverschlechterung zu verhindern.Photographic materials, particularly multi-layer color photographic materials, undergo a number of adverse changes during storage, including the loss of sensitivity and the increase in fog. These deficiencies occur particularly easily if the material contains layers that contain colloidal silver as a light-absorbing medium. Such layers are arranged, for example, as a silver filter yellow layer (according to Carey Lea) for absorbing unwanted blue light between the blue-sensitive and the green- and red-sensitive layers. In addition, a gray, black or blue colloidal silver-containing antihalation layer can be applied under the light-sensitive layers in order to prevent the backscattering of light into the light-sensitive layers and thus a deterioration in sharpness.

Der Vorteil von Silber als lichtabsorbierendes Medium gegenüber organischen Farbstoffen für Filterschichten besteht in der Regel darin, dass eine gleiche Absorptionswirkung mit wesentlich dünneren Schichten erzielt werden kann. Andererseits kann eine kolloidales Silber enthaltende Schicht die fotografischen Eigenschaften der benachbarten lichtempfindlichen Teilschichten nachteilig beeinflussen. Dieses kann sich insbesondere bei der Lagerung durch erhöhten Schleier und Empfindlichkeitsverlust bemerkbar machen.The advantage of silver as a light-absorbing medium over organic dyes for filter layers is usually that the same absorption effect can be achieved with much thinner layers. On the other hand, a layer containing colloidal silver can adversely affect the photographic properties of the adjacent light-sensitive partial layers. This can be particularly noticeable during storage due to increased fog and loss of sensitivity.

Zur Herabsetzung dieses Schleiers ist bekannt, Antischleiermittel (Antifoggants) den betreffenden Emulsionsschichten oder den kolloidales Silber enthaltenden Filterschichten zuzufügen. Brauchbare Antischleiermittel sind vor allem heterocyclische Verbindungen, wie Benzimidazole, Benztriazole und heterocyclische Mercaptoverbindungen, insbesondere 1-Phenyl-5-mercaptotetrazol und dessen 1-Amidophenyl- sowie 1-Ureidophenylderivate. Gemäss der DE-OS 1 547 694 und der US 3 397 987 soll durch Zusatz von Mercaptotetrazolen zu Silberhalogenidemulsionen, insbesondere zu verschleierten Silberhalogenidemulsionen, der Schleier bei Mischungen aus verschleierten und unverschleierten Emulsionen verhindert werden. Gemäss der DE-OS 1 942 883 und der US 3 708 303 soll die Punktqualität (Dot Quality) bei kontrastreichen Silberhalogenidemulsionen, die zu mindestens 50% aus Chlorid bestehen, durch Verwendung von Amidophenylmercaptotetrazolen verbessert werden, die z.B. einer lichtempfindlichen Emulsionsschicht oder einer zu dieser benachbart angeordneten Schicht einverleibt werden können. Bei diesen Aufzeichnungsmaterialien handelt es sich nicht um farbfotografische Aufzeichnungsmaterialien, sondern um Schwarzweiss-Materialien die mit ganz speziellen Entwicklern (Lith-Entwicklern) zu entwickeln sind. Aus der US 3 695 881 ist ein Verfahren zur Herstellung von Bildern bekannt, bei dem Jodidionen aus einer silberjodidhaltigen Emulsion die Löslichkeit einer anderen Emulsion, die mit einem Phenylmercaptotetrazol behandelt wurde, erhöht. Gemäss der DE-OS 2 437 353 und der GB 1 471 554 sollen Verunreinigungen durch Silber bei der Entwicklung von Schwarzweiss Materialien durch Entwicklung in Gegenwart von Amidophenylmercaptotetrazolen vermieden werden. Aus der DE-OS 2 336 721 und der US 3 945 829 ist bekannt, heterocyclische Mercaptoverbindungen in einer kolloidales Silber enthaltenden Schicht zur Verminderung des Schleiers zu verwenden. Gemäss der EP 0 080 631 sollen Ureidophenylmercaptotetrazole den Schleier bei fotografischen Materialien unterdrücken, ohne die Bleichbarkeit zu beeinträchtigen. Sie können z.B. in eine lichtempfindliche Schicht, eine kolloidales Silber enthaltende Schicht oder in eine Hilfsschicht eingebracht werden.To reduce this fog it is known to add antifoggants to the emulsion layers in question or the filter layers containing colloidal silver. Antifoggants which can be used are above all heterocyclic compounds, such as benzimidazoles, benzotriazoles and heterocyclic mercapto compounds, in particular 1-phenyl-5-mercaptotetrazole and its 1-amidophenyl and 1-ureidophenyl derivatives. According to DE-OS 1 547 694 and US Pat. No. 3,397,987, the addition of mercaptotetrazoles to silver halide emulsions, in particular to veiled silver halide emulsions, is intended to prevent the veil in the case of mixtures of veiled and unveiled emulsions. According to DE-OS 1 942 883 and US Pat. No. 3,708,303, the dot quality in high-contrast silver halide emulsions, which consist of at least 50% chloride, is to be improved by using amidophenyl mercaptotetrazoles, which e.g. a light-sensitive emulsion layer or a layer arranged adjacent to it can be incorporated. These recording materials are not color photographic recording materials, but black and white materials that are to be developed with very special developers (lith developers). No. 3,695,881 discloses a method for producing images in which iodide ions from an emulsion containing silver iodide increases the solubility of another emulsion which has been treated with a phenyl mercaptotetrazole. According to DE-OS 2 437 353 and GB 1 471 554, contamination by silver in the development of black and white materials should be avoided by development in the presence of amidophenyl mercaptotetrazoles. From DE-OS 2 336 721 and US 3 945 829 it is known to use heterocyclic mercapto compounds in a layer containing colloidal silver to reduce the fog. According to EP 0 080 631, ureidophenyl mercaptotetrazoles are intended to suppress the haze in photographic materials without impairing bleachability. You can e.g. in a light-sensitive layer, a layer containing colloidal silver or in an auxiliary layer.

Aus diversen Patentschriften (DE 2 163 546, US 3 715 208, US 3 705 802) und anderen ist bekannt, Mercaptoverbindungen als Bleichinhibitoren bei der Herstellung von Silbertonspuren zu verwenden.From various patents (DE 2 163 546, US 3 715 208, US 3 705 802) and others it is known to use mercapto compounds as bleach inhibitors in the production of silver tone traces.

Obwohl sich unter den vorgeschlagenen Verbindungen, insbesondere unter den Mercaptotetrazolderivaten, Antischleiermittel mit ausgezeichneter Wirkung befinden, haftet ihnen in der Reghel der schwerwiegende Nachteil an, dass sie die fotografische Empfindlichkeit mehr oder weniger stark herabsetzen, dass sie die Bleichung des entwickelten Silbers während der Verarbeitung behindern können oder dass sie durch Diffusion in lichtempfindliche Nachbarschichten dort zu nachteiligen Veränderungen der fotografischen Eigenschaften beitragen.Although antifoggants with excellent activity are among the proposed compounds, particularly mercaptotetrazole derivatives, they generally have the serious disadvantage that they reduce the photographic sensitivity to a greater or lesser extent by hindering the bleaching of the developed silver during processing or that they contribute to adverse changes in the photographic properties by diffusion into light-sensitive neighboring layers.

Aufgabe der Erfindung ist es, ein verbessertes farbfotografisches Material mit wenigstens einer lichtempfindlichen Silberhalogenidemulsionsschicht und wenigstens einer kolloidales Silber enthaltenden Schicht anzugeben, das diese Nachteile, insbesondere die Herabsetzung der fotografischen Empfindlichkeit, nicht in dem bekannten Mass aufweist.The object of the invention is to provide an improved color photographic material with at least one light-sensitive silver halide emulsion layer and at least one layer containing colloidal silver, which does not have these disadvantages, in particular the reduction in photographic sensitivity, to the known extent.

Es wurde nun ein farbtotografisches Auzeichnungsmaterial mit wenigstens einer lichtempfindlichen Silberhalogenidemulsionsschicht, wenigstens einer Schicht, die kolloidales Silber enthält und wenigstens einer zwischen diesen Schichten angeordneten silberfreien Schicht gefunden. Erfindungsgemäss enthält das Material in der silberfreien Schicht wenigstens ein Antischleiermittel folgender Formel

Figure imgb0001
worin bedeuten:

  • R1 Wasserstoff oder einen gegebenenfalls substituierten aliphatischen Rest mit 1 bis 6 C-Atomen
  • R2 einen n -wertigen gegebenenfalls substituierten aliphatischen Rest mit 4 bis 17 C-Atomen, wenn n für 1 steht und mit 2 bis 17 C-Atomen, wenn n für 2 steht
  • m 0 oder 1
  • n 1 oder 2
  • M Wasserstoff, Alkalimetallatom oder eine Ammoniumgruppe
  • Ar einen zweiwertigen, gegebenenfalls substituierten aromatischen Rest, insbesondere Phenylen und Naphthylen, z.B.
    Figure imgb0002
  • Het einen zweiwertigen heterocyclischen Rest, der wenigstens ein N-Atom enthält und der gegebenenfalls substituiert sein kann, insbesondere einen Rest mit oder aus einem Ringsystem mit 5 Ringgliedern, z.B. ein Thiazol, Selenazol, Imidazol, Oxadiazol, und insbesondere ein Triazol, Thiadiazol, Tetrazol, Oxazol.
We have now found a color photographic recording material with at least one light-sensitive silver halide emulsion layer, at least one layer which contains colloidal silver and at least one silver-free layer arranged between these layers. According to the invention, the material in the silver-free layer contains at least one antifoggant of the following formula
Figure imgb0001
 in which mean:
  • R 1 is hydrogen or an optionally substituted aliphatic radical having 1 to 6 carbon atoms
  • R 2 is an n-substituted, optionally substituted aliphatic radical having 4 to 17 carbon atoms if n is 1 and having 2 to 17 carbon atoms if n is 2
  • m 0 or 1
  • n 1 or 2
  • M is hydrogen, an alkali metal atom or an ammonium group
  • Ar is a divalent, optionally substituted aromatic radical, in particular phenylene and naphthylene, for example
    Figure imgb0002
  • Het is a divalent heterocyclic radical which contains at least one N atom and which can be optionally substituted, in particular a radical with or from a ring system with 5 ring members, for example a thiazole, selenazole, imidazole, oxadiazole, and in particular a triazole, thiadiazole, tetrazole , Oxazole.

In einer besonders bevorzugten Ausführungsform entsprechen die Antischleiermittel folgender Formel la

Figure imgb0003
worin die Substituenten die o.a. Bedeutung haben.In a particularly preferred embodiment, the antifoggants correspond to the following formula la
Figure imgb0003
 in which the substituents have the meaning given above.

Geeignete Substituenten für R1, R2, Ar und Het sind derartige, die für Antischleiermittel in lichtempfindlichen Silberhalogenidmaterialien geeignet sind, beispielsweise Hydroxy, Alkoxy, wie z.B. Methoxy oder Ethoxy, Halogen, wie Fluor, Chlor oder Brom. Insbesondere Het kann auch mit einem Aryl-, bevorzugt mit einem Phenylrest substituiert sein.Suitable substituents for R 1 , R 2 , Ar and Het are those which are suitable for antifoggants in light-sensitive silver halide materials, for example hydroxyl, alkoxy, such as, for example, methoxy or ethoxy, halogen, such as fluorine, chlorine or bromine. Het in particular can also be substituted with an aryl, preferably with a phenyl radical.

In einer bevorzugten Ausführungsform steht R1 für Wasserstoff oder einen Alkylrest. In einer weiteren bevorzugten Ausführungsform steht R2 für einen Alkylrest. M steht bevorzugt für Wasserstoff.In a preferred embodiment, R 1 is hydrogen or an alkyl radical. In a further preferred embodiment, R 2 represents an alkyl radical. M preferably represents hydrogen.

In einer besonders bevorzugten Ausführungsform weist das Aufzeichnungsmaterial wenigstens eine blauempfindliche, wenigstens eine grünempfindliche und wenigstens eine rotempfindliche Schicht auf. In einer bevorzugten Ausführungsform ist die kolloidales Silber enthaltende Schicht eine Gelbfilterschicht, wobei die silberfreie Schicht mit einer Verbindung I zwischen der Gelbfilterschicht und einer grün- oder rotempfindlichen Schicht angeordnet ist.In a particularly preferred embodiment, the recording material has at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive layer. In a preferred embodiment, the colloidal silver-containing layer is a yellow filter layer, the silver-free layer being arranged with a connection I between the yellow filter layer and a green- or red-sensitive layer.

In einer weiteren bevorzugten Ausführungsform weist das erfindungsgemässe Material jeweils wenigstens eine blau-, grün- und rotempfindliche Schicht sowie eine Antihalationsschicht mit kolloidalem Silber auf, wobei eine silberfreie Schicht mit der erfindungsgemäss zu verwendenden Verbindung 1 zwischen der Antihalationsschicht und den angegebenen Schichten angeordnet ist.In a further preferred embodiment, the material according to the invention each has at least one blue, green and red sensitive layer and an antihalation layer with colloidal silver, a silver-free layer with the compound 1 to be used according to the invention being arranged between the antihalation layer and the specified layers.

Die erfindungsgemäss zu verwendenden Verbindungen werden vorzugsweise in Mengen von 10-2 bis 10-8 Mol/m2, vorzugsweise in Mengen von 10-4 bis 10-6 Mol/m2 den silberfreien Schichten zugesetzt.The present invention compounds to be used are preferably used in amounts of from 10- 2 to 10- 8 mol / m 2, preferably in amounts of from 10- 4 to 10- 6 mol / m 2 of the silver-free layers added.

Typische erfindungsgemäss zu verwendende Verbindungen der oben angegebenen allgemeinen Formel sind in folgender Tabelle 1 angegeben.

Figure imgb0004
Figure imgb0005
Figure imgb0006
 Typical compounds of the general formula given above to be used according to the invention are given in Table 1 below.
Figure imgb0004
Figure imgb0005
Figure imgb0006

Mit dem erfindungsgemässen Material lassen sich farbige fotografische Bilder nach den verschiedensten Verfahren herstellen, z.B. nach dem Silberfarbbleichverfahrenn oder nach Farbdiffusionsverfahren. Besonders geeignet ist das erfindungsgemässe Material zur Erzeugung farbiger fotografischer Bilder durch chromogene Entwicklung in Anwesenheit von Farbkupplern, die mit dem Oxidationsprodukt von Entwicklern, im allgemeinen p-Phenylendiaminen, unter Bildung von Farbstoffen reagieren.With the material according to the invention, colored photographic images can be produced by a wide variety of processes, e.g. according to the silver color bleaching process or according to the color diffusion process. The material according to the invention is particularly suitable for producing colored photographic images by chromogenic development in the presence of color couplers which react with the oxidation product of developers, generally p-phenylenediamines, to form dyes.

Die Farbkuppler können dem Farbentwickler zugesetzt werden. In einer bevorzugten Ausführungsform enthält das fotografische Material selbst die üblichen Farbkuppler, die in der Regel den Silberhalogenidschichten einverleibt sind. So kann die rotempfindliche Schicht beispielsweise einen nicht-diffundierenden Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes enthalten, in der Regel einen Kuppler von Phenol- oder a-Naphtholtyp. Die grünempfindliche Schicht kann beispielsweise mindestens einen nichtdiffundierenden Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes enthalten, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons oder des Imidazolons Verwendung finden. Die blauempfindliche Schicht kann beispielsweise einen nicht-diffundierenden Farbkuppler zur Erzeugung des gelben Teilfarbenbildes, in der Regel einen Farbkuppler mit einer offenkettigen Ketomethylengruppierung enthalten. Bei den Farbkupplern kann es sich z.B. um 6-, 4- und um 2-Äquivalentkuppler handeln, darunter die sogenannten Weisskuppler die bei Reaktion mit Farbentwickleroxidationsprodukten keinen Farbstoff ergeben, sowie DIR-Kuppler. Geeignete Kuppler sind beispielsweise bekannt aus den Veröffentlichungen «Farbkuppler» von W. Pelz in «Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/München», Band 111, Seite 111 (1961), K. Venkataraman in «The Chemistry of Synthetic Dyes», Vol. 4, 341 bis 387, Academic Press (1971) und T.H. games, «The Theory of the Photographic Process», 4. Ed., S. 353-362, sowie aus der Research Disclosure Nr. 17643 vom Dezember 1978, Abschnitt VII.The color couplers can be added to the color developer. In a preferred embodiment, the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers. For example, the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or a-naphthol type. The green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used. The blue-sensitive layer can contain, for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping. The color couplers can e.g. are 6-, 4- and 2-equivalent couplers, including the so-called white couplers, which do not produce any dye when reacted with color developer oxidation products, and DIR couplers. Suitable couplers are known, for example, from the publications “Color Coupler” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Munich”, Volume 111, page 111 (1961), K. Venkataraman in “The Chemistry of Synthetic Dyes”, Vol. 4, 341 to 387, Academic Press (1971) and TH games, "The Theory of the Photographic Process", 4th Ed., pp. 353-362, and from Research Disclosure No. 17643 of December 1978, Section VII.

Die erfindungsgemässen farbfotografischen Aufzeichnungsmaterialien enthalten vorzugsweise wenigstens eine Silberhalogenidemulsionsschichten-Einheit für die Aufzeichnung von Licht jedes der drei Spektralbereiche Rot, Grün und Blau. Jede dieser Schichteinheiten kann eine einzige Silberhalogenidemulsionsschicht oder auch mehrere Silberhalogenidemulsionsschichten umfassen. Farbfotografische Aufzeichnungsmaterialien mit Doppelschichten für die verschiedenen Spektralbereiche sind beispielsweise aus den US-Patentschriften 3 663 228, 3 849 138 und 4 184 876 bekannt.The color photographic recording materials according to the invention preferably contain at least one silver halide emulsion layer unit for recording light from each of the three spectral ranges red, green and blue. Each of these layer units can comprise a single silver halide emulsion layer or also a plurality of silver halide emulsion layers. Color photographic recording materials with double layers for the different spectral ranges are known, for example, from US Pat. Nos. 3,663,228, 3,849,138 and 4,184,876.

Die verwendeten Silberhalogenidemulsionen können als Halogenid Chlorid, Bromid und Jodid bzw. Mischungen davon enthalten. In einer bevorzugten Ausführungsform besteht der Halogenidanteil wenigstens einer Schicht zu 0 bis 10 Mol-% aus Agl, zu 0 bis 10 Mol-% aus AgCI und zu 0 bis 100% aus AgBr, wobei sich die Summe dieser Anteile zu 100% ergänzt. In einer weiteren Ausführungsform kann der Halogenidanteil auch überwiegend aus Chlorid bestehen. Die Silberhalogenidhörner können z.B. kubisch, oktaedrisch oder tafelförmig sein.The silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide. In a preferred embodiment, the halide content of at least one layer consists of 0 to 10 mol% of Agl, 0 to 10 mol% of AgCl and 0 to 100% of AgBr, the sum of these proportions being 100%. In a further embodiment, the halide portion can also consist predominantly of chloride. The silver halide horns can e.g. be cubic, octahedral or tabular.

Die Emulsionen können in an sich bekannter Weise optisch sensibilisiert werden, z.B. mit den üblichen Polymethinfarbstoffen, wie Neutrocyaninen, basischen oder sauren Carbocyaninen, Rhodacyaninen, Hemicyaninen, Styrylfarbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind von F.M. Hamer in «The Cyanine Dyes and related Compounds», (1964), beschrieben. Verwiesen sei diesbezüglich insbesondere auf Ullmanns Enzyklopädie dertechnischen Chemie, 4. Auflage. Band 18, Seiten 431 ff und auf die oben angegebene Research Disclosure Nr. 17643, Abschnitt IV.The emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like. Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Chemical Engineering, 4th edition. Volume 18, pages 431 ff and on the above-mentioned Research Disclosure No. 17643, Section IV.

Zusätzlich zu den erfindungsgemäss zu verwendenden Antischleiermittel können üblicherweise verwendete Antischleiermittel und Stabilisatoren verwendet werden.In addition to the antifoggants to be used according to the invention, commonly used antifoggants and stabilizers can be used.

Als Stabilisatoren sind besonders geeignet Azaindene, vorzugsweise Tetra- oder Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind z.B. in dem Artikel von Birr, Z. Wiss. Phot. 47, 1952), S. 2-58, beschrieben. Weitere geeignete Stabilisatoren und Antischleiermittel sind in der oben angegebenen Research Disclosure Nr. 17643 in Abschnitt IV angegeben.Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are described, for example, in the article by Birr, Z. Wiss. Phot. 47, 1952), pp. 2-58. Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17643 above in Section IV.

Für die erfindungsgemässen Materialien können die üblichen Schichtträger verwendet werden, z.B. Träger aus Celluloseestern, z.B. Celluloseacetat und aus Polyestern. Geeignet sind ferner Papierträger, die gegebenenfalls beschichtet sein können z.B. mit Polyolefinen, insbesondere mit Polyethylen oder Polypropylen. Verwiesen wird diesbezüglich auf die oben angegebene Research Disclosure Nr. 17643 Abschnitt XVII.The usual layer supports can be used for the materials according to the invention, e.g. Cellulose ester supports, e.g. Cellulose acetate and polyester. Also suitable are paper supports, which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene. In this regard, reference is made to Research Disclosure No. 17643 section XVII indicated above.

Als Schutzkolloid bzw. Bindemittel für die Schichten des Aufzeichnungsmaterials sind die üblichen hydrophilen filmbildenden Mittel geeignet, z.B. Proteine, insbesondere Gelatine, Alginsäure oder deren Derivate wie Ester, Amide oder Salze, Cellulose-Derivate wie Carboxymethylcellulose und Cellulosesulfate, Stärke oder deren Derivate oder hydrophile synthetische Bindemittel wie Polyvinylalkohol, teilweise verseiftes Polyvinylacetat, Polyvinylpyrrolidon und andere. Die Schichten können im Gemisch mit den hydrophilen Bindemitteln auch andere synthetische Bindemittel in gelöster oder dispergierter Form enthalten wie Homo-oder Copolymerisate von Acryl- oder Methacrylsäure oder deren Derivaten wie Erstern, Amiden oder Nitrilen, ferner Vinylpolymerisate wie Vinylester oder Vinylether. Verwiesen wird weiterhin auf die in der oben angegebenen Research Disclosure 17643 in Abschnitt IX angegebenen Bindemittel.The usual hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others. In a mixture with the hydrophilic binders, the layers can also contain other synthetic binders in dissolved or dispersed form, such as homo- or copolymers of acrylic or methacrylic acid or their derivatives, such as first, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers. Reference is also made to the binders specified in Research Disclosure 17643 above in Section IX.

Die Schichten des fotografischen Materials können in der üblichen Weise gehärtet sein, beispielsweise mit Formaldehyd, mit Härtern des Epoxidtyps, des heterocyclischen Ethylenimins und des Acryloyltyps. Weiterhin ist es auch möglich, die Schichten gemäss dem Verfahren der deutschen Offenlegungsschrift 2 218 009 zu härten, um farbfotografische Materialien zu erzielen, die für eine Hochtemperaturverarbeitung geeignet sind. Es ist ferner möglich, die fotografischen Schichten bzw. die farbfotografischen Mehrschichtenmaterialien mit Härtern der Diazin-, Triazin-oder 1,2-Dihydrochinolin-Reihe zu härten oder mit Härtern vom Vinylsulfon-Typ.The layers of the photographic material can be hardened in the usual manner, for example with formaldehyde, with hardeners of the epoxy type, the heterocyclic ethyleneimine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German Offenlegungsschrift 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type.

Weitere geeignete Härter sind beispielsweise angegeben in der oben angegebenen Research Disclosure 17643 in Abschnitt XI.Further suitable hardeners are given, for example, in Research Disclosure 17643 given in Section XI.

Weitere geeignete Zusätze werden in der Research Disclosure 17643 und in «Product Licnsing Index» von Dezember 1971, Seiten 107-110 angegeben.Further suitable additives are given in Research Disclosure 17643 and in the "Product Licensing Index" from December 1971, pages 107-110.

Geeignete Farbentwicklersubstanzen für das erfindungsgemässe Material sind insbesondere solche vom p-Phenylendiamintyp, z.B. 4-Amino-N,N-diethyl-anilinhydrochlorid; 4-Amino-3-methyl-N-ethyl--N-ß-(methansulfonamido)-ethylanilinsulfathydrat; 4-Amino-3-methyl-N-ethyl-N-ß-hydroxy-ethyl-ani- linsulfat; 4-Amino-N-ethyl-N-(2-methoxyethyl)-m--toluidin-di-p-toluolsulfonsäure und N-Ethyl-N-ß-hydroxyethyl-p-phenylendiamin.Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl - N-β- (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N-ß-hydroxy-ethyl-aniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine.

Weitere brauchbare Farbentwickler sind beispielsweise beschrieben in J. Amer. Chem. Soc. 73, 3100 (1951) und in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seiten 545 ff.Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73, 3100 (1951) and ff in G. Haist, Modern Photogra p hic Processing, 1979, John Wiley and Sons, New York, pp 545th

Nach der Farbentwicklung wird das Material üblicherweise gebleicht und fixiert. Bleichung und Fixierung können getrennt voneinander oder auch zusammen durchgeführt werden. Als Bleichmittel können die üblichen Verbindungen verwendet werden, z.B. Fell-Salze und Fe3+-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe usw. Besonders bevorzugt sind Eisen-III-Komplexe von Aminopolycarbonsäuren, insbesondere z.B. Ethylendiamintetraessigsäure, Nitrilotriessigsäure, lminodiessigsäure, N-Hydroxyethylethylendiamintriessigsäure, Alkyliminodicarbonsäuren und von entsprechenden Phosphonsäuren. Geeignet als Bleichmittel sind weiterhin Persulfate.After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, for example fur salts and Fe 3 + complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, lminodiacetic acid, N-hydroxyethylethylenediamine diamine , Alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.

Beispiel 1example 1

Auf einen mit einer Lichthofschutzschicht und einer Haftschicht versehenen Cellulosetriacetatträger werden nacheinander die im folgenden angegebenen Schichten aufgetragen. Angegebene Mengenangaben beziehen sich jeweils auf 1 m2. Der Silberauftrag wird durch die Angabe der äquimolaren Mengen Silbernitrat ausgewiesen:The layers specified below are applied in succession to a cellulose triacetate support provided with an antihalation layer and an adhesive layer. The stated quantities relate to 1 m 2 . The silver application is indicated by specifying the equimolar amounts of silver nitrate:

1. Rotempfindliche Schicht geringer Empfindlichkeit1. Red sensitive layer of low sensitivity

Die Schicht enthält eine Silberbromidjodidemulsion (6 Mol % Silberjodid), einen Blaugrünkuppler, einen DIR-Kuppler sowie einen Maskenkuppler. Silberauftrag: 3,4 g.The layer contains a silver bromide iodide emulsion (6 mol% silver iodide), a cyan coupler, a DIR coupler and a mask coupler. Silver application: 3.4 g.

2. Rotempfindliche Schicht hoher Empfindlichkeit2. Red sensitive layer of high sensitivity

Die Schicht enthält eine Silberbromidjodidemulsion mit 10 Mol % Silberjodid sowie einen Blaugrünkuppler. Silberauftrag: 2,2 g.The layer contains a silver bromide iodide emulsion with 10 mol% silver iodide and a cyan coupler. Silver application: 2.2 g.

3. Zwischenschicht3rd intermediate layer

Die Zwischenschicht enthält 0,7 g Gelatine, 0,09 g eines darin dispergierten Fängers für Entwickleroxidationsprodukte der folgenden Formel:

Figure imgb0007
The intermediate layer contains 0.7 g of gelatin, 0.09 g of a scavenger for developer oxidation products of the following formula dispersed therein:
Figure imgb0007

4. Grünempfindliche Schicht geringer Empfindlichkeit4. Green sensitive layer of low sensitivity

Die Schicht enthält eine Silberbromidjodidemulsion (6 Mol % Silberjodid) sowie einen Purpurkuppler vom Pyrazolontyp, einen DIR-Kuppler und einen Gelbmaskenkuppler. Silberauftrag: 2,2 g.The layer contains a silver bromide iodide emulsion (6 mol% silver iodide) as well as a purple coupler of the pyrazolone type, a DIR coupler and a yellow mask coupler. Silver application: 2.2 g.

5. Grünempfindliche Schicht hoher Empfindlichkeit5. Green sensitive layer of high sensitivity

Die Schicht enthält eine Silberbromidjodidemulsion (10 Mol % Silberjodid) sowie einen darin dispergierten Purpurkuppler vom Pyrazolontyp.The layer contains a silver bromide iodide emulsion (10 mol% silver iodide) and a purple coupler of the pyrazolone type dispersed therein.

6. Zwischenschicht6. Interlayer

Die Zwischeschicht enthält 0, 5 g Gelatine und darin dispergiert den unter Schicht 3 angegebenen Fänger für Entwickleroxidationsprodukte sowie gegebenenfalls die in der folgenden Tabelle 2 angegebenen Antischleiermittel.The intermediate layer contains 0.5 g of gelatin and disperses therein the scavenger for developer oxidation products indicated under layer 3 and optionally the antifoggants indicated in Table 2 below.

7. Gelbfilterschicht7. Yellow filter layer

Die Gelbfilterschicht enthält kolloidales Silber. Dichte: 0,7.The yellow filter layer contains colloidal silver. Density: 0.7.

8. Blauempfindliche Schicht niedriger Empfindlichkeit8. Blue sensitive layer of low sensitivity

Die Schicht enthält eine Silberbromidjodidemulsion (5 Mol % Silberjodid) und darin dispergiert eine Abmischung von Gelbkupplern vom Benzoylacetanilid-Typ.The layer contains a silver bromide iodide emulsion (5 mol% silver iodide) and dispersed therein a mixture of yellow couplers of the benzoylacetanilide type.

9. Blauempfindliche Schicht hoher Empfindlichkeit9. Blue sensitive layer of high sensitivity

Die Schicht enthält eine blauempfindliche Schicht mit 6 Mol % Silberjodid sowie eine Mischung der unter Schicht 8 angegebenen Gelbkuppler.The layer contains a blue-sensitive layer with 6 mol% of silver iodide and a mixture of the yellow couplers indicated under layer 8.

10. UV-Absorberschicht10. UV absorber layer

Die Schicht enthält in Gelatine dispergiert 0,8 g eines UV-Absorbers vom Benzotriazol-Typ.The layer contains 0.8 g of a benzotriazole-type UV absorber dispersed in gelatin.

11. Deckschicht11. Top layer

Die Deckschicht besteht aus gehärteter Gelatine.The top layer consists of hardened gelatin.

Proben derart aufgebauter Materialien werden hinter einem Stufenkeil belichtet und einer üblichen Farbnegativverarbeitung, wie sie beschrieben wurde in British Journal of Photography, 1974, Seite 597, unterworfen.Samples of materials constructed in this way are exposed behind a step wedge and subjected to the usual color negative processing as described in British Journal of Photography, 1974, page 597.

Vor der Auswertung wurden die Proben zur Überprüfung der Lagerstabilität folgenden Lagerbedingungen A ausgesetzt: 7 Tage Lagerung bei einer Temperatur von 35% °C, 90% relativer Feuchtigkeit und unter Lichtausschluss.Before the evaluation, the samples were subjected to the following storage conditions A to check their storage stability: 7 days storage at a temperature of 35% ° C, 90% relative humidity and with exclusion of light.

Verglichen wurden die so erhaltenen Werte mit den Werten die erhalten wurden nach einer Lagerung unter normalen Bedingungen B: 7 Tage Lagerung bei einer Temperatur von 20°C und 60% relativer Feuchtigkeit. Aus folgender Tabelle 2 sind die Veränderungen infolge der Lagerung unter den Bedingungen A verglichen mit der Lagerung B angegeben (jeweils Empfindlichkeits- bzw. Schleierdifferenz B-A):

Figure imgb0008
The values thus obtained were compared with the values obtained after storage under normal conditions B: storage for 7 days at a temperature of 20 ° C. and 60% relative humidity. The following table 2 shows the changes due to storage under conditions A compared to storage B (in each case sensitivity or fog difference BA):
Figure imgb0008

Es ist deutlich zu sehen, dass bei Zusatz der erfindungsgemäss zu verwendenden Verbindungen 1 bis 7 ein deutlich geringerer Empfindlichkeitsverlust und eine deutlich geringere Schleierzunahme auftritt als bei Abwesenheit dieser Verbindungen.It can be clearly seen that when compounds 1 to 7 to be used according to the invention are added, there is a significantly lower loss of sensitivity and a significantly lower increase in fog than when these compounds are absent.

Beispiel 2Example 2

Gemäss dem in Beispiel 1 angegebenen allgemeinen Aufbauschema wurden fünf verschiedene Aufbauten bis Q hergestellt, die sich dadurch unterschieden, dass in der unter 6. angegebenen Zwischenschicht zwischen der Gelbfilterschicht und der grünempfindlichen Schicht hoher Empfindlichkeit die in folgender Tabelle 3 angegebenen Verbindungen zugesetzt wurden.According to the general construction scheme given in Example 1, five different assemblies to Q were produced, which differed in that the compounds listed in Table 3 below were added in the intermediate layer indicated under 6 between the yellow filter layer and the green-sensitive layer of high sensitivity.

Figure imgb0009
Figure imgb0009

Aus Beispiel 2 ist zu ersehen, dass mit zunehmender Menge der erfindungsgemäss zu verwendenden Verbindungen die bei Lagerung A auftretende Schleierzunahme abnimmt.It can be seen from Example 2 that with increasing amount of the compounds to be used according to the invention, the increase in fog which occurs during storage A decreases.

Beispiel 3Example 3

Es wird ein Aufzeichnungsmaterial gemäss Beispiel 1, Aufbau A hergestellt, wobei aber in die Haftschicht zwischen der Lichthofschutzschicht aus kolloidalem Silber und der rotempfindlichen Schicht geringer Empfindlichkeit die in folgender Tabelle 4 angegebenen erfindungsgemäss zu verwendenden Verbindungen eingebracht wurden. Das Material wird wie in Beispiel 1 beschrieben unter den Lagerungsbedingungen A und B gelagert, belichtet und dann wie in Beispiel 1 angegeben entwickelt.

Figure imgb0010
A recording material according to Example 1, Structure A is produced, but the compounds to be used according to the invention which are indicated in Table 4 below were introduced into the adhesive layer between the antihalation layer made of colloidal silver and the red-sensitive layer of low sensitivity. The material is stored as described in Example 1 under storage conditions A and B, exposed and then developed as indicated in Example 1.
Figure imgb0010

Aus den Ergebnissen der Tabelle 4 lässt sich ersehen, dass durch Einlagerung einer erfindungsgemäss zu verwendenden Verbindung in die Haftschicht eine deutliche Schleierstabilität im Blaugrün-Schichtpaket zu verzeichnen ist sowie geringerer Empfindlichkeitsrückgang.It can be seen from the results in Table 4 that by incorporating a compound to be used according to the invention in the adhesive layer, there is significant fog stability in the cyan layer package and a lower decrease in sensitivity.

Claims (10)

1. A colour-photographic recording material which has at least one photosensitive silver halide emulsion layer, at least one layer which contains colloidal silver and at least one silver-free layer positioned between these layers, characterised in that the silver-free layer contains at least one anti-foggant corresponding to the following formula:
Figure imgb0013
wherein
R1 represents hydrogen or an optionally substituted aliphatic radical having from 1 to 6 carbon atoms,
R2 represente an n-valent, optionally substituted aliphatic radical having from 4 to 17 carbon atoms when n represents 1, and having from 2 to 17 carbon atoms when n represents 2,
m represents 0 or 1,
n represents 1 or 2,
M represents hydrogen, an alkali metal atom or an ammonium group,
Ar represents a bivalent optionally substituted aromatic radical,
Het represents a bivalent heterocyclic radical containing at least one N-atom and which may be substituted.
2. A material according to claim 1, characterised in that the anti-foggant corresponds to the following formula
Figure imgb0014
wherein the substituents are defined as in claim 1.
3. A material according to claim 1, characterised in that it contains at least one colour coupler.
4. A material according to claim 1, characterised in that it contains at least one blue-sensitive layer, at least one green-sensitive layer and at least one red-sensitive layer, the layer containing colloidal silver is a yellow filter layer, and the silver-free layer is positioned between the yellow filter layer and a green-sensitive layer or a red-sensitive layer.
5. A material according to claim 1, characterised in that it contains at least one blue-, green- and red-sensitive layer and an anti-halation layer consisting of colloidal silver, and the silver-free layer is positioned between the anti-halation and the other layers.
6. A material according to claim 1, characterised in that it contains the compound corresponding to formula I in a quantity of from 10-2 to 10-8 mol/mz.
7. A material according to claim 1, characterised in that it contains the compound corresponding to formula I in a quantity of from 10-4 to 10-6 mol/m2.
8. A material according to claim 1, characterised in that at least one photosensitive silver halide emulsion layer is divided into at least two partial layers which differ in sensitivity.
9. A material according to claim 1, characterised in that the silver halide of the photosensitive silver halide emulsion layer consists of 0-10 mol % of silver iodide, 0-10 mol % of silver chloride and 0-100 mol % of silver bromide, the total of these proportions amounting to 100%. -
10. A material according to claim 1, characterised in that the photosensitive silver halide emulsion layer mainly contains silver bromide as silver halide.
EP84110240A 1983-09-10 1984-08-29 Colour-photographic recording material Expired EP0141128B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3332688 1983-09-10
DE19833332688 DE3332688A1 (en) 1983-09-10 1983-09-10 COLOR PHOTOGRAPHIC RECORDING MATERIAL

Publications (3)

Publication Number Publication Date
EP0141128A2 EP0141128A2 (en) 1985-05-15
EP0141128A3 EP0141128A3 (en) 1986-01-22
EP0141128B1 true EP0141128B1 (en) 1988-04-20

Family

ID=6208726

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84110240A Expired EP0141128B1 (en) 1983-09-10 1984-08-29 Colour-photographic recording material

Country Status (4)

Country Link
US (1) US4576907A (en)
EP (1) EP0141128B1 (en)
JP (1) JPS6073627A (en)
DE (2) DE3332688A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4957855A (en) * 1989-09-21 1990-09-18 Eastman Kodak Company Photographic recording material with improved raw stock keeping
JPH03202849A (en) * 1989-12-28 1991-09-04 Konica Corp Silver halide photographic sensitive material for laser light source
DE69205263T2 (en) * 1991-12-19 1996-05-15 Eastman Kodak Co Reversal photographic element and its processing method.
JP6655449B2 (en) * 2016-03-30 2020-02-26 株式会社日本触媒 Squarylium compounds

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1445324A (en) * 1964-09-01 1966-07-08 Eastman Kodak Co New mercaptoterazoles and their use as overdevelopment inhibitors in the processing of color photographic materials
DE1935310C3 (en) * 1968-07-15 1974-02-07 Fuji Photo Film Co. Ltd., Ashigara, Kanagawa (Japan) Process for developing a color photographic recording material
US3695881A (en) * 1970-11-25 1972-10-03 Eastman Kodak Co Positive image production with unfogged internal image silver halide emulsion containing mercaptan retarder and a surface latent image silver halide emulsion
DE2308530A1 (en) * 1973-02-21 1974-08-29 Agfa Gevaert Ag METHOD FOR CONTROLLING THE DEVELOPMENT OF COLOR INVERSION FILMS
DE2336721A1 (en) * 1973-07-19 1975-02-06 Agfa Gevaert Ag COLOR PHOTOGRAPHIC MULTI-LAYER MATERIAL WITH IMPROVED COLOR DENSITY
JPS5037436A (en) * 1973-08-03 1975-04-08
JPS5559463A (en) * 1978-10-30 1980-05-02 Konishiroku Photo Ind Co Ltd Color photographic material
US4448878A (en) * 1981-11-13 1984-05-15 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials

Also Published As

Publication number Publication date
EP0141128A2 (en) 1985-05-15
DE3470613D1 (en) 1988-05-26
DE3332688A1 (en) 1985-03-28
US4576907A (en) 1986-03-18
EP0141128A3 (en) 1986-01-22
JPS6073627A (en) 1985-04-25

Similar Documents

Publication Publication Date Title
DE3687606T2 (en) METHOD FOR TREATING A COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL.
EP0154920B1 (en) Emulsion with a high silver chloride content, photographic registration material and process for obtaining a photograhic registration
EP0152822B1 (en) Photographic recording material
EP0148441B1 (en) Colour-photographic recording material and developing process
EP0040771B1 (en) Photographic material and its use in the formation of images
DE3420173C2 (en)
DE69113492T2 (en) Photographic recording material.
EP0141128B1 (en) Colour-photographic recording material
DE4039022A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL
EP0157322B1 (en) Photographic recording material, process for stabilizing a photographic recording material and triazoles
DE3626219A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH A YELLOW DIR COUPLER
EP0234392A2 (en) Photographic-recording material and process for making photographic images
EP0188202B1 (en) Photographic recording material and process for making photographic images
EP0345514A2 (en) Colour photographic silver halide material
DE3418749C2 (en)
DE3803664A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL FOR THE PRODUCTION OF COLORED SUPERVISORY PICTURES
DE3545611A1 (en) LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIAL
DE69108037T2 (en) PHOTOGRAPHIC MATERIAL.
DE3601227A1 (en) PHOTOGRAPHIC RECORDING MATERIAL, METHOD FOR PRODUCING PHOTOGRAPHIC IMAGES AND NEW TRIAZOLES
DE3805348A1 (en) METHOD FOR PRODUCING COLORED PICTURES AND COLOR PHOTOGRAPHIC RECORDING MATERIAL SUITABLE THEREOF
DE4000844A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL
DE3706202A1 (en) Colour-photographic recording material
DE3838467A1 (en) Photographic recording material
DE2827937A1 (en) PHOTOGRAPHIC MATERIAL WITH LATENT IMAGE STABILIZERS
DE4418511A1 (en) Colour print material giving good inter:image effect without increasing silver content

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19840829

AK Designated contracting states

Designated state(s): BE DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): BE DE FR GB

17Q First examination report despatched

Effective date: 19861027

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: AGFA-GEVAERT AG

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB

REF Corresponds to:

Ref document number: 3470613

Country of ref document: DE

Date of ref document: 19880526

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: DE

Payment date: 19900731

Year of fee payment: 7

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

Ref country code: GB

Payment date: 19900803

Year of fee payment: 7

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

Ref country code: FR

Payment date: 19900816

Year of fee payment: 7

Ref country code: BE

Payment date: 19900816

Year of fee payment: 7

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

Ref country code: GB

Effective date: 19910829

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

Ref country code: BE

Effective date: 19910831

BERE Be: lapsed

Owner name: AGFA-GEVAERT A.G.

Effective date: 19910831

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19920430

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

Ref country code: DE

Effective date: 19920501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST