EP0011051A2 - Colour-photographic recording material, process for its stabilisation and production of colour-photographic images - Google Patents

Colour-photographic recording material, process for its stabilisation and production of colour-photographic images Download PDF

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Publication number
EP0011051A2
EP0011051A2 EP79810141A EP79810141A EP0011051A2 EP 0011051 A2 EP0011051 A2 EP 0011051A2 EP 79810141 A EP79810141 A EP 79810141A EP 79810141 A EP79810141 A EP 79810141A EP 0011051 A2 EP0011051 A2 EP 0011051A2
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Prior art keywords
carbon atoms
alkyl
color photographic
light
recording material
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German (de)
French (fr)
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EP0011051B1 (en
EP0011051A3 (en
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David G. Dr. Leppard
Michael Dr. Rasberger
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Novartis AG
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Ciba Geigy AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/3924—Heterocyclic
    • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
    • G03C7/39248—Heterocyclic the nucleus containing only nitrogen as hetero atoms one nitrogen atom

Definitions

  • the present invention relates to a color photographic recording material which contains at least one light stabilizer in at least one light-sensitive silver halide emulsion layer and / or in at least one of the customary auxiliary layers.
  • color photographic recording materials which contain color couplers in light-sensitive silver halide emulsion layers are known to be exposed and developed with an aromatic developer containing primary amino groups.
  • the oxidized developer substance then reacts with the color coupler to form an image dye, the amount of which depends on the amount of incident light.
  • a multilayer photographic light-sensitive material is used which consists of a red-sensitive layer containing the cyan coupler, a green-sensitive layer containing the magenta coupler, and a blue-sensitive layer which in turn contains the yellow coupler.
  • the corresponding dyes with the colors blue-green, purple and yellow are created.
  • Phenols or a-naphthols are usually used as cyan couplers, pyrazolones as magenta couplers and acylacetylamides as yellow couplers.
  • the dyes formed after development are accordingly indophenols, indamines or azomethines.
  • the ultraviolet absorbers In order to achieve adequate light protection, however, relatively large amounts of the ultraviolet absorbers must be used, which generally has the consequence that the thickness of the photographic layers into which the ultraviolet absorbers are incorporated must be increased. Such a measure is highly undesirable for the photographic properties of the material. In addition, the ultraviolet absorbers do not provide effective protection against fading of color images by visible light.
  • Another disadvantage of using relatively large amounts of ultraviolet absorbers is that large amounts of solvent are required in order to achieve the desired fine distribution of these compounds in the aqueous binder emulsions. If concentrated solutions of the ultraviolet absorbers are used, there is a risk that they will become uncontrolled when incorporated into the binder emulsions, ie not in the separate the desired fine distribution and so uniform protection against ultraviolet radiation cannot be achieved.
  • the present invention therefore relates to a color photographic recording material which contains at least one piperidine compound as light stabilizer in at least one light-sensitive silver halide emulsion layer, an intermediate layer and / or a protective layer, characterized in that the piperidine compound of the formula in which R 1 is hydrogen or alkyl having 1 to 4 carbon atoms, R 2 is alkyl or hydroxyalkyl each having 1 to 12 carbon atoms, alkenyl or alkynyl having 3 or 4 carbon atoms, benzyl or R6CO-, in which R 6 is hydrogen, alkyl having 1 up to 12 carbon atoms, alkenyl with 2 or 3 carbon atoms, chloromethyl, cyclohexyl, benzyl or optionally substituted phenyl or phenylethyl with two alkyl groups each with 1 to 4 carbon atoms and a hydroxyl group, R 3 is hydrogen or methyl, R 4 and R 5 per alkyl with 1 to 5 carbon atoms or cycl
  • the light stabilizers can also be used in combination with conventional ultraviolet absorbers.
  • the present invention furthermore relates to a process for stabilizing color photographic recording materials by incorporating at least one light stabilizer of the formula (1), if appropriate in combination with an ultraviolet absorber, into at least one light-sensitive and / or auxiliary layer of the material, a process for the preparation of the harmful action light-stabilized color photographic images by imagewise exposure and color development of the aforementioned recording materials and the color photographic images thus obtained.
  • R 1 is alkyl with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl or n-butyl. Ethyl and especially methyl are preferred.
  • R 2 is alkyl having 1 to 12 carbon atoms
  • primary alkyl groups such as those mentioned above, as well as, for example, n-amyl, n-hexyl, n-octyl, n-nonyl, n-decyl or n-dodecyl are generally suitable.
  • the analogous residues apply to hydroxyalkyl.
  • R 2 in the meaning alkenyl or alkynyl with 3 or 4 carbons can be, for example, allyl, methallyl or propargyl.
  • R 2 are alkyl or hydroxyalkyl each having 1 to 4 carbon atoms, alkenyl or alkynyl having 3 or 4 carbon atoms, benzyl and also acyl, where formyl, acetyl, propionyl, acrylyl, methacrylyl, crotonyl, benzoyl or benzylcarbonyl can be mentioned.
  • R 3 is hydrogen or methyl.
  • R 4 and R 5 are each alkyl having 1 to 5 carbon atoms, the primary alkyl radicals already mentioned above, and also secondary and tertiary alkyl groups, such as isopropyl, isobutyl or tert. Butyl are suitable.
  • R 4 and R 5 are also cycloalkyl having 5 to 8 carbon atoms, such as, in particular, in particular cyclopentyl and cyclohexyl.
  • Preferred meanings of R 4 and R are alkyl having 1 to 4 carbon atoms, in particular methyl and tert. Butyl.
  • the substituent Y as an optionally present substituent on the central carbon atom in the compounds of the formula (1) can be hydrogen, straight-chain or branched alkyl having 1 to 12 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, n-amyl, n-hexyl, n- and iso-heptyl, n-octyl, n-nonyl, n-decyl, n-jndecyl or Dodecyl and the corresponding isomers.
  • Y has the meaning - (CH 2 ) q COOR 7 , in which q is 0 or an integer from 1 to 10, hydrogen, methyl or ethyl are suitable for R 7 .
  • R 8 is methyl or ethyl, furthermore phenyl or benzyl; Y is also cyan, benzyl or a radical of the formulas (la) or (1b); wherein the substituents have the meanings given.
  • the substituent R 9 in the formula (Ib) has the meaning hydrogen, methyl or ethyl.
  • Color photographic recording materials which have at least one compound of the formula as light stabilizers are now preferred contain, wherein R 10 is methyl, ethyl, benzyl, acetyl, acrylyl, methacrylyl, crotonyl, allyl or propargyl.
  • the compounds of the formulas (1) to ( 31 ) are known compounds which are described, for example, in DE-OS 2 456 364, 2 647 452, 2 654 058 and 2 656 76 9 .
  • the compounds can be prepared by various methods, with several reaction steps generally being required.
  • Starting materials for the first reaction stage are, for example, malonic acid or one of its reactive derivatives, such as the di ' alkyl esters, and 4-hydroxy- or 4-aminopiperidines, the substituents (R 2 ) on the nitrogen atom of the piperidine ring already in the molecule can be present or can be introduced into the molecule in a later N-alkylation or N-acylation step by customary methods.
  • Suitable alkylating or acylating agents are, for example, alkyl halides, alkenyl halides, propargyl chloride, benzyl chloride or carboxylic acid chlorides, which are preferably reacted with the piperidine derivative in the presence of molar amounts of a base. Hydroxyalkyl residues are introduced into the molecule by reaction with epoxides, for example ethylene oxide or propylene oxide.
  • the compounds of formula (1) can either be introduced first with the hydroxybenzyl substituent and then with the substituent Y or - preferably - first with the substituent Y and then with the hydroxybenzyl group.
  • the hydroxybenzyl group can be introduced by reaction with an alkyl-substituted hydroxybenzyldithiocarbamate of the formula HO-benzyl-S-CS-N (R ") 2 , where R" is an alkyl group having 1 to 5 carbon atoms or both groups R "together with the nitrogen represent a morpholine, pyrrolidine or piperidine ring.
  • R " is an alkyl group having 1 to 5 carbon atoms or both groups R "together with the nitrogen represent a morpholine, pyrrolidine or piperidine ring.
  • dithiocarbamates can be obtained by reacting a phenol with formaldehyde, carbon disulfide and a secondary amine.
  • substituent Y is present in the compounds of the formulas (1) and (2), it can be introduced into the molecule by the known methods of C-alkylation of activated methylene compounds.
  • the compounds of formulas (1) and (2) are hardly soluble in water, and therefore they are in a low boiling organic solvent such as methyl acetate, ethyl acetate, carbon tetrachloride, chloroform, methanol, ethanol, n- h utanol, dioxane, acetone or benzene , a high-boiling organic solvent, such as tricresyl phosphate, dimethylformamide, dimethyl sulfoxide, di-n-butyl phthalate or ethyl-N-diphenylcarbamate, or a solvent mixture of the above-mentioned low-boiling and high-boiling organic solvents, the solution obtained becomes a protective colloid solution, in particular an aqueous gelatin solution and dispersed by means of a colloid mill of a homogenizer or by using ultrasound.
  • a protective colloid solution in particular an aqueous gelatin solution and dispersed by means of
  • the dispersions thus obtained are then used to produce the layers of color photographic recording materials (for example film, paper or silver color bleaching materials).
  • These layers can, for example, be intermediate or protective layers, but in particular light-sensitive (blue and red-sensitive) silver halide emulsion layers, in which the cyan, cyan, magenta and yellow dyes are formed from the corresponding color couplers during the development of the exposed recording material will.
  • ultraviolet absorbers are also used, they are located in the same layers, but preferably in the intermediate or protective layers.
  • the light stabilizer can also be applied in the treatment baths that are used after the color development, e.g. in fixing and / or washing baths, although a certain solubility of the compounds of the formula (1) in alcohols, (methanol / ethanol) aqueous alkali and / or water is required.
  • the light stabilizer can be incorporated not only into the usual photographic emulsion layers, but also into a receiving layer.
  • Any cyan, purple and yellow couplers that are used to form the dyes mentioned and thus the color images can be used. You can e.g. be dissolved in an alkaline solution or in a high-boiling organic solvent, these solutions then being dispersed in an aqueous gelatin solution and incorporated into a photographic silver halide emulsion.
  • the silver halide emulsions preferably contain gelatin as a binder, optionally in a mixture with other high-molecular natural or synthetic compounds.
  • the silver halide emulsions can for example be silver bromide, silver chloride or silver iodide emulsions or also those emulsions which contain a mixture of silver halides, e.g. Silver bromide-iodide or silver chloride-bromide emulsions.
  • the emulsions can be chemically sensitized, they can also contain conventional organic stabilizers and antifoggants and also conventional plasticizers, such as e.g. Glycerin.
  • the emulsions can also be hardened with the hardeners customary for gelatin.
  • the emulsions may also contain conventional casting aids.
  • the emulsions can be applied to conventional supports for photographic recording material.
  • the usual developer baths can be used to develop the color photographic recording material. These typically contain a p-phenylenediamine type developer, a development retardant such as potassium bromide, an antioxidant such as sodium sulfite and a base e.g. an alkali hydroxide or alkali carbonate.
  • the developing baths may also contain a conventional antifoggant and complexing agent.
  • the amount of the light stabilizer can vary within wide limits and is approximately in the range from 1 to 500 mg, preferably 1 to 300 and in particular 200 mg per m 2 of the layer into which it (they) is (are) incorporated.
  • the ultraviolet absorber can be present together with the light stabilizer in one layer or in an adjacent layer.
  • the weight ratio between a conventional ultraviolet absorber and the light stabilizer of the formula (1) is approximately (5-10): 1, the molar ratio approximately (10-20): 1.
  • Examples of ultraviolet absorbers are e.g. Compounds of the benzophenone, acrylonitrile, thiazolidone, benztriazole, oxazole, thiazole and imidazole type.
  • the color images obtained with the recording material according to the invention by exposure and development show a clearly improved light fastness to visible and ultraviolet light.
  • the compounds of formula (1) are practically colorless, so that there is no discoloration of the images; in addition, they are well compatible with the usual photographic additives present in the individual layers; Because of their good effectiveness, their use amount can be reduced and thus their precipitation or crystallization is avoided if they are incorporated as an organic solution in the aqueous binder emulsions used for the production of photographic layers.
  • the individual processing steps required to produce the color images after exposure of the photographic recording material are not adversely affected by the light stabilizers. Furthermore, the so-called pressure fog formation that frequently occurs with blue-sensitive emulsions can be largely suppressed. This can e.g.
  • 7.0 ml of 6% gelatin solution and 0.5 ml of an 8% solution of the wetting agent of the formula are added in isopropanol / water (3: 4) and 0.5 ml of water, then emulsified with the aid of an ultrasound device and with a power of 100 watts, for 5 minutes 2.5 ml of freshly sonicated coupler additive emulsion, 0.8 ml of silver bromide emulsion containing 2.8% silver, 0.7 ml of a 1% aqueous solution of the hardener of the formula 0.4 ml of a 1.5% aqueous gelatin solution and 4.0 ml of water are mixed together, adjusted to a pH of 6.5 and poured onto a substrate glass plate of 13x18 cm format at 40 ° C. After the layer has solidified at 10 ° C., the plate is dried in a drying cabinet with circulating air at room temperature.
  • a strip of the coated glass plate cut to a format of 4.0 cm x 6.5 cm is exposed to 500 lux for 6 seconds under a step wedge and then processed at 32.8 ° C ( ⁇ 0.3 ° C) as follows:
  • the developer bath has the following composition:
  • the pH is 10.1.
  • a conventional bath which has the following composition, for example, serves as the bleach-fix bath.
  • the step wedge obtained in this way is irradiated in an Atlas device (lamp 2500 W) with 10,000 Langley units each, with and without an ultraviolet filter (Kodak filter 2C).
  • the data show the good protection of the photographic material against the harmful influence of light, which can be achieved when using the light stabilizers used according to the invention.
  • the effects are significantly improved compared to those that can be achieved with known light stabilizers already used in photographic materials.
  • Good results are also achieved with the compounds of the formulas (4), (6), (8) to (22) and (24) to (3 1 ).
  • 0.4 ml of 1.5% aqueous gelatin solution and 4.0 ml of water are mixed with one another, adjusted to a pH of 6.5 and poured at 40 ° C. onto a 13 x 18 cm format glass plate. After the layer has solidified at 10 ° C., the plate is dried in a drying cabinet with ambient air at room temperature.
  • a strip of the coated glass plate cut to a format of 4.0 cm ⁇ 6.5 cm is exposed under a step wedge at 500 lux for 6 seconds and then at 32.8 ° C. ( ⁇ 0.3 ° C.) as in Example 1 described processed.
  • a clear, sharp, blue-green colored step wedge is obtained with an absorption maximum at 653 nm and a maximum density of 1.10.
  • step wedge and step wedges produced analogously, which were produced using the compounds (105) to (110), are exposed and measured as described in Example 1. Table 2 contains the results.
  • Analog other photographic materials are prepared, each dissolved in addition to the color coupler ol light stabilizers in amounts of 0,7.10 -3 M and 1.4 x 10 -3 mol per m 2 in Essigester contain.
  • Gelatin solutions are prepared as in Example 1, but the light stabilizers of the formulas (23) (according to the invention) and (105) and (106) (comparison) and the yellow coupler of the formula are used or the formula (DE-OS 2 757 380).
  • the light stabilizers and the yellow couplers are used in a molar ratio of 1: 1.
  • Example 1 The production of the coated glass plates, the exposure and photographic processing and the light fastness test are carried out as in Example 1.
  • the light fastness test is carried out with an irradiation of 15,000 Langley units.

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  • Physics & Mathematics (AREA)
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  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

Farbphotographisches Auzeichnungsmaterial, das in mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, einer Zwischenschicht und/oder einer Schutzschicht mindestens eine Piperidinverbindung mit einer oder mehreren alkylsubstituierten Phenolgruppen als Lichtschutzmittel enthält. Farbilder, die durch bildmässige Belichtung und Entwicklung dieses farbphotographischen Aufzeichnungsmaterials erhalten werden, zeigen eine gute Stabilität gegen die Einwirkung von sichtbarem und ultraviolettem Licht.Color photographic recording material which contains at least one piperidine compound with one or more alkyl-substituted phenol groups as light stabilizers in at least one light-sensitive silver halide emulsion layer, an intermediate layer and / or a protective layer. Color images obtained by imagewise exposure and development of this color photographic recording material show good stability against the action of visible and ultraviolet light.

Description

Die vorliegende Erfindung betrifft ein farbphotographisches Aufzeichnungsmaterial, das in mirdestens einer lichtempfindlichen Silberhalogenidemulsionsschicht und/oder in mindestens einer der üblichen Hilfsschichten mindestens.ein'Lichtschutzmittel enthält.The present invention relates to a color photographic recording material which contains at least one light stabilizer in at least one light-sensitive silver halide emulsion layer and / or in at least one of the customary auxiliary layers.

Zur Herstellung farbphotographischer Bilder werden bekanntlich farbphotographische Aufzeichnungsmaterialien, die in lichtempfindlichen Silberhalogenid-Emulsionsschichten gleichzeitig Farbkuppler enthalten, belichtet und mit einer aromatischen, primäre Aminogruppen enthaltenden Entwicklersubstanz entwickelt. Die oxydierte Entwicklersubstanz reagiert dann mit dem Farbkuppler unter Bildung eines Bildfarbstoffes, wobei dessen Menge von der Menge des eingefallenen Lichtes abhängig ist. Im allgemeinen wird ein lichtempfindliches photographisches Mehrschichtenmaterial verwendet, das. aus einer rotempfindlichen Schicht, die den Blaugrünkuppler enthält, einer grünempfindlichen Schicht, die den Purpurkuppler enthält, und einer blauempfindlichen Schicht, die ihrerseits den Gelbkuppler enthält, besteht. Bei der Farbentwicklung entstehen dann die entsprechenden Farbstoffe mit den Farben blaugrün, purpur und gelb.For the production of color photographic images, color photographic recording materials which contain color couplers in light-sensitive silver halide emulsion layers are known to be exposed and developed with an aromatic developer containing primary amino groups. The oxidized developer substance then reacts with the color coupler to form an image dye, the amount of which depends on the amount of incident light. In general, a multilayer photographic light-sensitive material is used which consists of a red-sensitive layer containing the cyan coupler, a green-sensitive layer containing the magenta coupler, and a blue-sensitive layer which in turn contains the yellow coupler. During the color development, the corresponding dyes with the colors blue-green, purple and yellow are created.

Gewöhnlich werden als Blaugrünkuppler Phenole oder a-Naphthole, als Purpurkuppler Pyrazolone und als Gelbkuppler Acylacetylamide eingesetzt. Die nach der Entwicklung gebildeten Farbstoffe sind dementsprechend Indophenole, Indamine oder Azomethine.Phenols or a-naphthols are usually used as cyan couplers, pyrazolones as magenta couplers and acylacetylamides as yellow couplers. The dyes formed after development are accordingly indophenols, indamines or azomethines.

Die Lichtechtheit dieser Farbstoffe und damit auch die der erhaltenen farbphotographischen Bilder sowohl gegenüber ultravioletten als auch gegenüber sichtbarem Licht ist allerdings unbefriedigend.However, the lightfastness of these dyes, and therefore also that of the color photographic images obtained, both in relation to ultraviolet and to visible light, is unsatisfactory.

Es sind deshalb bereits Verfahren bekannt geworden, um die farbphotographischen Bilder gegen die besonders schädliche Wirkung des Ultraviolettstrahlung (Wellenlängenbereich von etwa 300 bis 400 nm) durch Einarbeitung von Ultraviolettabsorbern in die photographischen Materialien zu schützen (DE-AS A547863).Methods have therefore already become known for protecting the color photographic images against the particularly harmful effect of ultraviolet radiation (wavelength range from about 300 to 400 nm) by incorporating ultraviolet absorbers into the photographic materials (DE-AS A547863).

Zur Erzielung eines ausreichenden Lichtschutzes müssen allerdings relativ grosse Mengen der Ultraviolettabsorber eingesetzt werden, was in der Regel zur Folge hat, dass die Dicke der photographischen Schichten, in die die Ultraviolettabsorber eingearbeitet werden, erhöht werden muss. Für die photographischen Eigenschaften des Materials ist eine solche Massnahme jedoch höchst unerwünscht. Ein wirksamer Schutz gegen das Ausbleichen von Farbbildern durch sichtbares Licht wird durch die Ultraviolettabsorber ausserdem nicht erreicht.In order to achieve adequate light protection, however, relatively large amounts of the ultraviolet absorbers must be used, which generally has the consequence that the thickness of the photographic layers into which the ultraviolet absorbers are incorporated must be increased. Such a measure is highly undesirable for the photographic properties of the material. In addition, the ultraviolet absorbers do not provide effective protection against fading of color images by visible light.

Ein weiterer Nachteil der Verwendung relativ grosser Mengen von Ultraviolettabsorbern besteht darin, dass man grosse Lösungsmittelmengen braucht, um die erwünschte Feinverteilung dieser Verbindungen in den wässrigen Bindemittelemulsionen zu erreichen. Setzt man konzentrierte Lösungen der Ultraviolettabsorber ein, so besteht die Gefahr, dass sie sich bei der Einarbeitung in die Bindemittelemulsionen unkontrolliert, d. h. nicht in der erwünschten Feinverteilung abscheiden und so ein gleichmässiger Schutz gegen ultraviolette Strahlung nicht erreicht werden kann.Another disadvantage of using relatively large amounts of ultraviolet absorbers is that large amounts of solvent are required in order to achieve the desired fine distribution of these compounds in the aqueous binder emulsions. If concentrated solutions of the ultraviolet absorbers are used, there is a risk that they will become uncontrolled when incorporated into the binder emulsions, ie not in the separate the desired fine distribution and so uniform protection against ultraviolet radiation cannot be achieved.

Auch die Neigung von Farbbildern, die unter Verwendung von Kupplern vom Pyrazolon- oder Phenoltyp gebildet werden, während der Lagerung Farbschleier zu bilden, wird durch die Ultraviolettabsorber nicht ausreichend verhindert.Also, the tendency of color images formed using pyrazolone or phenol type couplers to color fog during storage is not sufficiently prevented by the ultraviolet absorbers.

Aus den DE-OS 2126187 und 2126954 werden als geeignete Verbindungen gegen das Ausbleichen von Farbphotographien spezielle Piperidinderivate vorgeschlagen. Der Lichtschutz/der sowohl gegen sichtbares als auch gegen ultraviolettes Licht erreicht werden soll, ist allerdings nur gering und vermag die gestellten Anforderungen nicht zu erfüllen.From DE-OS 2126187 and 2126954 special piperidine derivatives are proposed as suitable compounds against the fading of color photographs. However, the light protection / which is to be achieved against visible as well as against ultraviolet light is only slight and cannot meet the requirements.

Aufgabe der vorliegenden Erfindung ist es daher, ein neues farbphotographisches Aufzeichnungsmaterial bereitzustellen, das besser wirksame Lichtschutzmittel sowohl gegen sichtbares als auch gegen ultraviolettes Licht enthält, um so die Lichtechtheit der aus diesen photographischen Aufzeichnungsmaterialien erhaltenen Farbbilder weiter zu verbessern (ein Ausbleichen der Farbstoffe zu verhindern) und ausserdem die unerwünschte Schleierbildung zu unterdrücken.It is therefore an object of the present invention to provide a new color photographic recording material which contains more effective light stabilizers against both visible and ultraviolet light in order to further improve the light fastness of the color images obtained from these photographic recording materials (to prevent the dyes from fading). and also to suppress unwanted fog.

Es wurde nun überraschenderweise gefunden, dass man die gestellte Aufgabe erfindungsgemäss dadurch lösen kann, dass man die Verbindungen der Formel (1), gegebenenfalls in Kombination mit bekannten Ultraviolettabsorbern, in relativ kleinen Mengen in farbphotographische Aufzeichnungsmaterialien einarbeitet und so einen wirkungsvollen , dem Stand der Technik überlegenen Lichtschutz erreicht.It has now surprisingly been found that the object can be achieved according to the invention by incorporating the compounds of the formula (1), if appropriate in combination with known ultraviolet absorbers, in relatively small amounts into color photographic recording materials and thus an effective, state of the art superior light protection achieved.

Gegenstand der vorliegenden Erfindung ist daher ein farbphotographisches Aufzeichnungsmaterial, das in mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, einer Zwischenschicht und/oder einer Schutzschicht mindestens eine Piperidinverbindung als Lichtschutzmittel enthält, dadurch gekennzeichnet, dass die Piperidinverbindung der Formel

Figure imgb0001
entspricht, worin R1 Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen ist, R2 Alkyl oder Hydroxyalkyl mit je 1 bis 12 Kohlenstoffatomen, Alkenyl oder Alkinyl mit 3 oder 4 Kohlenstoffatomen, Benzyl oder R6CO- ist, worin R6 Wasserstoff, Alkyl mit 1 bis 12 Kohlenstoffatomen, Alkenyl mit 2 oder 3 Kohlenstoffatomen, Chlormethyl, Cyclohexyl, Benzyl oder gegebenenfalls mit zwei Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen und einer Hydroxylgruppe substituiertes Phenyl oder Phenyläthyl ist, R3 Wasserstoff oder Methyl ist, R4 und R5 je Alkyl mit 1 bis 5 Kohlenstoffatomen oder Cycloalkyl mit 5 bis 8 Kohlenstoffatomen sind, Y Wasserstoff, Alkyl mit 1 bis 12 Kohlenstoffatomen, -CnH2nCOOR7, worin n 0 oder eine ganze Zahl von 1 bis 10 und R7 Wasserstoff, Alkyl mit 1 bis 18 Kohlenstoffatomen, insbesondere Methyl oder Aethyl oder der Rest der Formel
Figure imgb0002
ist, worin R1 und R2 die angegebenen Bedeutungen haben, oder Y -CH2CH2CN, -NHCOR8, worin R8 Methyl, Aethyl, Phenyl oder Benzyl ist, Y ferner Cyan, Benzyl oder ein Rest der Formel
Figure imgb0003
worin R1 und R2 die angegebenen Bedeutungen haben, Rg Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen, insbesondere Methyl oder Aethyl, m 1 oder 2 und p 1 oder 0 ist.The present invention therefore relates to a color photographic recording material which contains at least one piperidine compound as light stabilizer in at least one light-sensitive silver halide emulsion layer, an intermediate layer and / or a protective layer, characterized in that the piperidine compound of the formula
Figure imgb0001
 in which R 1 is hydrogen or alkyl having 1 to 4 carbon atoms, R 2 is alkyl or hydroxyalkyl each having 1 to 12 carbon atoms, alkenyl or alkynyl having 3 or 4 carbon atoms, benzyl or R6CO-, in which R 6 is hydrogen, alkyl having 1 up to 12 carbon atoms, alkenyl with 2 or 3 carbon atoms, chloromethyl, cyclohexyl, benzyl or optionally substituted phenyl or phenylethyl with two alkyl groups each with 1 to 4 carbon atoms and a hydroxyl group, R 3 is hydrogen or methyl, R 4 and R 5 per alkyl with 1 to 5 carbon atoms or cycloalkyl with 5 to 8 carbon atoms, Y is hydrogen, alkyl with 1 to 12 carbon atoms, -C n H 2n COOR 7 , where n is 0 or an integer from 1 to 10 and R 7 is hydrogen, alkyl with 1 to 18 carbon atoms, especially methyl or ethyl or the rest of the formula
Figure imgb0002
 is in which R 1 and R 2 have the meanings indicated, or Y -CH 2 CH 2 CN, -NHCOR 8 , in which R 8 is methyl, ethyl, phenyl or benzyl, Y furthermore cyan, benzyl or a radical of the formula
Figure imgb0003
 wherein R 1 and R 2 have the meanings given, Rg is hydrogen, alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl, m is 1 or 2 and p is 1 or 0.

Gegebenenfalls können die'Lichtschutzmittel auch in Kombination mit Ublichen Ultraviolettabsorbern eingesetzt werden. Gegenstand der vorliegenden Erfindung sind ferner ein Verfahren zur Stabilisierung farbphotographischer Aufzeichnungsmaterialien durch Einarbeitung mindestens eines Lichtschutzmittels der Formel (1), gegebenenfalls in Kombination mit einem Ultraviolettabsorber, in mindestens eine lichtempfindliche und/oder Hilfsschicht des Materials, ein Verfahren zur Herstellung von gegen die schädliche Einwirkung von Licht stabilisierten photographischen Farbbildern durch bildmässige Belichtung und Farbentwicklung der genannten Aufzeichnungsmaterialien sowie die so erhaltenen photographischen Farbbilder. In den Verbindungen der Formel (1) ist R1 je Alkyl mit 1 bis 4 Kohlenstoffatomen, wie z.B. Methyl, Aethyl, n-Propyl oder n-Butyl. Aethyl und insbesondere Methyl sind bevorzugt.If necessary, the light stabilizers can also be used in combination with conventional ultraviolet absorbers. The present invention furthermore relates to a process for stabilizing color photographic recording materials by incorporating at least one light stabilizer of the formula (1), if appropriate in combination with an ultraviolet absorber, into at least one light-sensitive and / or auxiliary layer of the material, a process for the preparation of the harmful action light-stabilized color photographic images by imagewise exposure and color development of the aforementioned recording materials and the color photographic images thus obtained. In the compounds of formula (1) R 1 is alkyl with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl or n-butyl. Ethyl and especially methyl are preferred.

Ist R2 Alkyl mit 1 bis 12 Kohlenstoffatomen, so kommen in der Regel primäre Alkylgruppen wie die vorstehend genannten, ferner z.B. n-Amyl, n-Hexyl, n-Octyl, n-Nonyl, n-Decyl oder n-Dodecyl in Frage. Für die Bedeutung Hydroxyalkyl gelten die analogen Reste.If R 2 is alkyl having 1 to 12 carbon atoms, primary alkyl groups such as those mentioned above, as well as, for example, n-amyl, n-hexyl, n-octyl, n-nonyl, n-decyl or n-dodecyl are generally suitable. For the meaning The analogous residues apply to hydroxyalkyl.

R2 in der Bedeutung Alkenyl oder Alkinyl mit 3 oder 4 Kohlenstoffen kann z.B. Allyl, Methallyl oder Propargyl sein.R 2 in the meaning alkenyl or alkynyl with 3 or 4 carbons can be, for example, allyl, methallyl or propargyl.

Hat R2 die Bedeutung Acyl (R6CO-), so kann R6 Wasserstoff, Alkyl mit 1 bis 12 Kohlenstoffatomen [Alkylgruppen wie vorstehend genannt, dazu gegebenenfalls auch isomere (verzweigtkettige) Alkylreste], Alkenyl mit 2 oder 3 Kohlenstoffatomen, wie z.B. CH2=CH-, CH2=C(CH3)- oder CH3CH=CH- ferner Chlormethyl, Cyclohexyl, Benzyl oder gegebenenfalls mit 2 Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen und einer Hydroxylgruppe substituiertes Phenyl oder Phenyläthyl sein.If R 2 is acyl (R 6 CO-), then R 6 can be hydrogen, alkyl having 1 to 12 carbon atoms [alkyl groups as mentioned above, and optionally also isomeric (branched-chain) alkyl radicals], alkenyl having 2 or 3 carbon atoms, for example CH 2 = CH-, CH 2 = C (CH 3 ) - or CH 3 CH = CH- also chloromethyl, cyclohexyl, benzyl or optionally substituted with 2 alkyl groups each with 1 to 4 carbon atoms and a hydroxyl group, phenyl or phenylethyl.

Bevorzugte Bedeutungen von R2 sind Alkyl oder Hydroxyalkyl mit je 1 bis 4 Kohlenstoffatomen, Alkenyl oder Alkinyl mit 3 oder 4 Kohlenstoffatomen, Benzyl und ferner Acyl, wobei Formyl, Acetyl, Propionyl, Acrylyl, Methacrylyl, Crotonyl, Benzoyl oder Benzylcarbonyl zu nennen sind.Preferred meanings of R 2 are alkyl or hydroxyalkyl each having 1 to 4 carbon atoms, alkenyl or alkynyl having 3 or 4 carbon atoms, benzyl and also acyl, where formyl, acetyl, propionyl, acrylyl, methacrylyl, crotonyl, benzoyl or benzylcarbonyl can be mentioned.

R3 ist Wasserstoff oder Methyl. R4 und R5 sind jeweils Alkyl mit 1 bis 5 Kohlenstoffatomen, wobei die vorstehend bereits genannten primären Alkylreste, ferner auch sekundäre und tertiäre Alkylgruppen, wie z.B. Isopropyl, Isobutyl oder tert. Butyl geeignet sind. R4 und R5 sind ferner Cycloalkyl mit 5 bis 8 Kohlenstoffatomen, wie z.B. insbesondere Cyclopentyl und Cyclohexyl. Bevorzugte Bedeutungen von R4 und R sind Alkyl mit 1 bis 4 Kohlenstoffatomen, insbesondere Methyl und tert. Butyl.R 3 is hydrogen or methyl. R 4 and R 5 are each alkyl having 1 to 5 carbon atoms, the primary alkyl radicals already mentioned above, and also secondary and tertiary alkyl groups, such as isopropyl, isobutyl or tert. Butyl are suitable. R 4 and R 5 are also cycloalkyl having 5 to 8 carbon atoms, such as, in particular, in particular cyclopentyl and cyclohexyl. Preferred meanings of R 4 and R are alkyl having 1 to 4 carbon atoms, in particular methyl and tert. Butyl.

Der Substituent Y als gegebenenfalls vorhandener Substituent am zentralen Kohlenstoffatom in den Verbindungen der Formel (1) kann Wasserstoff, geradkettiges oder verweigtes Alkyl mit 1 bis 12 Kohlenstoffatomen sein, wie z.B. Methyl, Aethyl, Propyl, iso-Propyl, Butyl, n-Amyl, n-Hexyl, n- und iso-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Jndecyl- oder Dodecyl und die entsprechenden Isomeren.The substituent Y as an optionally present substituent on the central carbon atom in the compounds of the formula (1) can be hydrogen, straight-chain or branched alkyl having 1 to 12 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, n-amyl, n-hexyl, n- and iso-heptyl, n-octyl, n-nonyl, n-decyl, n-jndecyl or Dodecyl and the corresponding isomers.

Hat Y die Bedeutung -(CH2)qCOOR7, worin q 0 oder eine ganze Zahl von 1 bis 10 ist, so kommen für R7 Wasserstoff, Methyl oder Aethyl in Frage. Stellt Y den Rest -NHCOR8 dar, so ist R8 Methyl oder Aethyl, ferner Phenyl oder Benzyl; Y ist ausserdem Cyan, Benzyl oder ein Rest der Formeln (la) oder (1b); worin die Substituenten die angegebenen Bedeutungen haben. Der Substituent R9 in der Formel (lb) hat die Bedeutung Wasserstoff, Methyl oder Aethyl.If Y has the meaning - (CH 2 ) q COOR 7 , in which q is 0 or an integer from 1 to 10, hydrogen, methyl or ethyl are suitable for R 7 . If Y represents -NHCOR 8 , R 8 is methyl or ethyl, furthermore phenyl or benzyl; Y is also cyan, benzyl or a radical of the formulas (la) or (1b); wherein the substituents have the meanings given. The substituent R 9 in the formula (Ib) has the meaning hydrogen, methyl or ethyl.

Bevorzugt sind nun solche farbphotographischen Aufzeichnungsmaterialien, die als Lichtschutzmittel mindestens eine Verbindung der Formel

Figure imgb0004

enthalten, worin R10 Methyl, Aethyl, Benzyl, Acetyl, Acrylyl, Methacrylyl, Crotonyl, Allyl oder Propargyl ist.Color photographic recording materials which have at least one compound of the formula as light stabilizers are now preferred
Figure imgb0004
contain, wherein R 10 is methyl, ethyl, benzyl, acetyl, acrylyl, methacrylyl, crotonyl, allyl or propargyl.

Typische Vertreter von Verbindungen der Formeln (1) und (2) sind die nachfolgenden Verbindungen

Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
 Typical representatives of compounds of the formulas (1) and (2) are the following compounds
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033

Bei den Verbindungen der Formeln (1) bis (31) handelt es sich um bekannte Verbindungen, die z.B. in den DE-OS 2 456 364, 2 647 452, 2 654 058 und 2 656 769 beschrieben sind.The compounds of the formulas (1) to ( 31 ) are known compounds which are described, for example, in DE-OS 2 456 364, 2 647 452, 2 654 058 and 2 656 76 9 .

Die Herstellung der Verbindungen kann nach verschiedenen Methoden erfolgen, wobei in der Regel mehre e Reaktionsschritte erforderlich sind.The compounds can be prepared by various methods, with several reaction steps generally being required.

Ausgangsmaterialien für die erste Reaktionsstufe.sind z.B. die Malonsäure, bzw. eines ihrer reaktionsfähigen Derivate, wie beispielsweise die Di'alkylester, und 4-Hydroxy- bzw. 4-Aminopiperidine, wobei die Substituenten (R2) am Stickstoffatom des Piperidinrings bereits im Molekül vorhanden sein können oder in einem späteren N-Alkylierungs- oder N-Acylierungsschritt nach üblichen Methoden in das Molekül eingeführt werden können. Geeignete Alkylierungs- bzw. Acylierungsmittel sind beispielsweise Alkylhalogenide, Alkenylhalogenide,Propargylchlorid, Benzylchlorid oder Carbonsäurechloride, die vorzugsweise in Gegenwart molarer 'Mengen einer Base mit dem Piperidinderivat umgesetzt werden. Hydroxyalkylreste werden durch Umsetzung mit Epoxyden, beispielsweise Aethylenoxyd oder Propylenoxyd, in das Molekül eingeführt.Starting materials for the first reaction stage are, for example, malonic acid or one of its reactive derivatives, such as the di ' alkyl esters, and 4-hydroxy- or 4-aminopiperidines, the substituents (R 2 ) on the nitrogen atom of the piperidine ring already in the molecule can be present or can be introduced into the molecule in a later N-alkylation or N-acylation step by customary methods. Suitable alkylating or acylating agents are, for example, alkyl halides, alkenyl halides, propargyl chloride, benzyl chloride or carboxylic acid chlorides, which are preferably reacted with the piperidine derivative in the presence of molar amounts of a base. Hydroxyalkyl residues are introduced into the molecule by reaction with epoxides, for example ethylene oxide or propylene oxide.

Als nächster Schritt kann in die Verbindungen der Formel (1) entweder zuerst der Hydroxybenzylsubstituent und anschliessend der Substituent Y eingeführt werden oder - vorzugsweise - zuerst der Substituent Y und dann die Hydroxybenzylgruppe.As a next step, the compounds of formula (1) can either be introduced first with the hydroxybenzyl substituent and then with the substituent Y or - preferably - first with the substituent Y and then with the hydroxybenzyl group.

Die Einführung der Hydroxybenzylgruppe kann durch Umsetzung mit einem alkylsubstituierten Hydroxybenzyldithiocarbamat der Formel HO-Benzyl- S-CS-N(R")2 geschehen, wobei R" eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen bedeutet oder beide Gruppen R" zusammen mit dem Stickstoff einen Morpholin-, Pyrrolidin- oder Piperidinring darstellen. Solche Dithiocarbamate sind durch Umsetzung eines Phenols mit Formaldehyd, Schwefelkohlenstoff und einem sekundären Amin erhältlich.The hydroxybenzyl group can be introduced by reaction with an alkyl-substituted hydroxybenzyldithiocarbamate of the formula HO-benzyl-S-CS-N (R ") 2 , where R" is an alkyl group having 1 to 5 carbon atoms or both groups R "together with the nitrogen represent a morpholine, pyrrolidine or piperidine ring. Such dithiocarbamates can be obtained by reacting a phenol with formaldehyde, carbon disulfide and a secondary amine.

Sofern der Substituent Y in den Verbindungen der Formeln (1) und (2) vorhanden ist, kann er nach den bekannten Methoden der C-Alkylierung von aktivierten Methylenverbindungen in das Molekül eingeführt werden.If the substituent Y is present in the compounds of the formulas (1) and (2), it can be introduced into the molecule by the known methods of C-alkylation of activated methylene compounds.

Die Verbindungen der Formeln (1) und (2) sind in Wasser kaum löslich, und sie werden deshalb in einem niedrigsiedenden organischen Lösungsmittel, wie Methylacetat, Aethylacetat, Tetrachlorkohlenstoff, Chloroform, Methanol, Aethanol, n-hutanol, Dioxan, Aceton oder Benzol, einem hochsiedenden organischen Lösungsmittel, wie Tricresylphosphat, Dimethylformamid, Dimethylsulfoxid, Di-n-butylphthalat oder Aethyl-N-diphenylcarbamat, oder einem Lösungsmittelgemisch aus den oben erwähnten niedrigsiedenden und hochsiedenden .organischen Lösungsmitteln gelöst, die erhaltene Lösung wird zu einer Schutzkolloidlösung, wie insbesondere einer wässrigen Gelatinelösung gegeben und mittels einer Kolloidmühle eines Homogenisators oder durch Anwendung von Ultraschall dispergiert.The compounds of formulas (1) and (2) are hardly soluble in water, and therefore they are in a low boiling organic solvent such as methyl acetate, ethyl acetate, carbon tetrachloride, chloroform, methanol, ethanol, n- h utanol, dioxane, acetone or benzene , a high-boiling organic solvent, such as tricresyl phosphate, dimethylformamide, dimethyl sulfoxide, di-n-butyl phthalate or ethyl-N-diphenylcarbamate, or a solvent mixture of the above-mentioned low-boiling and high-boiling organic solvents, the solution obtained becomes a protective colloid solution, in particular an aqueous gelatin solution and dispersed by means of a colloid mill of a homogenizer or by using ultrasound.

Die so erhaltenen Dispersionen werden dann zur Herstellung der Schichten von farbphotographischen Aufzeichnungsmaterialien (z.B. Film-, Papier- oder Silberfarbbleichmaterialien) verwendet. Diese Schichten können z.B. Zwischen- oder Schutzschichten, insbesondere jedoch lichtempfindliche (blau- und rotempfindliche) Silberhalogenidemulsionsschichten sein, in denen bei der Entwicklung des belichteten Aufzeichnungsmaterials aus den entsprechenden Farbkupplern, die Blaugrün-(Cyan)-, Purpur (Magenta)- und Gelbfarbstoffe gebildet werden.The dispersions thus obtained are then used to produce the layers of color photographic recording materials (for example film, paper or silver color bleaching materials). These layers can, for example, be intermediate or protective layers, but in particular light-sensitive (blue and red-sensitive) silver halide emulsion layers, in which the cyan, cyan, magenta and yellow dyes are formed from the corresponding color couplers during the development of the exposed recording material will.

Werden Ultraviolettabsorber mitverwendet so befinden sie sich in den gleichen Schichten, vorzugsweise jedoch in den Zwischen- oder Schutzschichten.If ultraviolet absorbers are also used, they are located in the same layers, but preferably in the intermediate or protective layers.

Gegebenenfalls kann das Lichtschutzmittel auch in den Behandlungsbädern appliziert werden, die nach der Farbentwicklung verwendet werden, z.B. in Fixier- und/oder Waschbädern, wobei jedoch eine gewisse Löslichkeit der Verbindungen der Formel (1) in Alkoholen , (Methanol/Aethanol) wässrigem Alkali und/oder Wasser erforderlich ist.If necessary, the light stabilizer can also be applied in the treatment baths that are used after the color development, e.g. in fixing and / or washing baths, although a certain solubility of the compounds of the formula (1) in alcohols, (methanol / ethanol) aqueous alkali and / or water is required.

Wenn die Diffusionstransfermethode angewandt wird, kann das Lichtschutzmittel nicht nur in die üblichen photographischen Emulsionsschichten, sondern auch in eine Empfangsschicht eingearbeitet werden.When the diffusion transfer method is used, the light stabilizer can be incorporated not only into the usual photographic emulsion layers, but also into a receiving layer.

Beliebige Blaugrün-, Purpur- und Gelb-Kuppler, die zur Bildung der genannten Farbstoffe und damit der Farbbilder verwendet werden, können eingesetzt werden. Sie können z.B. in alkalischer Lösung oder in einem hochsiedenden organischen Lösungsmittel gelöst werden, wobei dann diese Lösungen in einer wässrigen Gelatinelösung dispergiert und in eine photographische Silberhalogenidemulsion eingearbeitet werden.Any cyan, purple and yellow couplers that are used to form the dyes mentioned and thus the color images can be used. You can e.g. be dissolved in an alkaline solution or in a high-boiling organic solvent, these solutions then being dispersed in an aqueous gelatin solution and incorporated into a photographic silver halide emulsion.

Die Silberhalogenidemulsionen enthalten als Bindemittel vorzugsweise Gelatine, gegebenenfalls im Gemisch mit anderen hochmolekularen natürlichen oder synthetischen Verbindungen.The silver halide emulsions preferably contain gelatin as a binder, optionally in a mixture with other high-molecular natural or synthetic compounds.

Die Silberhalogenidemulsionen können beispielsweise Silberbromid-, Silberchlorid- oder Silberjodidemulsionen oder auch solche Emulsionen sein, die ein Gemisch von Silberhalogeniden enthalten, wie z.B. Silberbromid-jodid-oder Silberchlorid-bromidemulsionen.The silver halide emulsions can for example be silver bromide, silver chloride or silver iodide emulsions or also those emulsions which contain a mixture of silver halides, e.g. Silver bromide-iodide or silver chloride-bromide emulsions.

Die Emulsionen können chemisch sensibilisiert werden, sie können ferner übliche organische Stabilisatoren und Antischleiermittel sowie auch übliche Weichmacher, wie z.B. Glycerin, enthalten. Die Emulsionen können ferner mit den für Gelatine üblichen Härtungsmitteln gehärtet werden. Ferner können die Emulsionen übliche Giesshilfsmittel enthalten. Die Emulsionen können auf übliche Schichtträger für photographisches Aufzeichnungsmaterial aufgebracht werden.The emulsions can be chemically sensitized, they can also contain conventional organic stabilizers and antifoggants and also conventional plasticizers, such as e.g. Glycerin. The emulsions can also be hardened with the hardeners customary for gelatin. The emulsions may also contain conventional casting aids. The emulsions can be applied to conventional supports for photographic recording material.

Zur Entwicklung des farbenphotographischen Aufzeichnungsmaterials können die üblichen Entwicklerbäder eingesetzt werden. Diese enthalten in der Regel eine Entwicklersubstanz des p-Phenylendiamin-Typs, einen Entwicklungsverzögerer, wie Kaliumbromid, ein Antioxydationsmittel, wie Natriumsulfit, und eine Base, z.B. ein Alkalihydroxyd oder Alkalicarbonat. Ferner können die Entwicklungsbäder ein übliches Antischleiermittel und Komplexbildner enthalten.The usual developer baths can be used to develop the color photographic recording material. These typically contain a p-phenylenediamine type developer, a development retardant such as potassium bromide, an antioxidant such as sodium sulfite and a base e.g. an alkali hydroxide or alkali carbonate. The developing baths may also contain a conventional antifoggant and complexing agent.

Die Menge des Lichtschutzmittels, gegebenenfalls in Kombination mit einem üblichen Ultraviolettabsorber, kann in weiten Grenzen schwanken und liegt etwa im Bereich von 1 bis 500 mg, vorzugsweise 1 bis.300 und insbesondere 200 mg pro m2 der Schicht, in die es (sie) eingearbeitet wird(werden).The amount of the light stabilizer, if appropriate in combination with a conventional ultraviolet absorber, can vary within wide limits and is approximately in the range from 1 to 500 mg, preferably 1 to 300 and in particular 200 mg per m 2 of the layer into which it (they) is (are) incorporated.

Der Ultraviolettabsorber kann mit dem Lichtschutzmittel zusammen in einer Schicht oder auch in einer benachbarten Schicht vorhanden sein. Das Gewichtsverhältnis zwischen einem üblichen Ultraviolettabsorber und dem Lichtschutzmittel der Formel (1) beträgt etwa (5-10):1, das molare Verhältnis etwa (10-20):1. Beispiele .für Ultraviolett-Absorber sind z.B. Verbindungen vom Benzophenon-, Acrylnitril-, Thiazolidon-, Benztriazol-, Oxazol-, Thiazol- und Imidazoltyp.The ultraviolet absorber can be present together with the light stabilizer in one layer or in an adjacent layer. The weight ratio between a conventional ultraviolet absorber and the light stabilizer of the formula (1) is approximately (5-10): 1, the molar ratio approximately (10-20): 1. Examples of ultraviolet absorbers are e.g. Compounds of the benzophenone, acrylonitrile, thiazolidone, benztriazole, oxazole, thiazole and imidazole type.

Die'mit dem erfindungsgemässen Aufzeichnungsmaterial durch Belichtung und Entwicklung erhaltenen Farbbilder zeigen eine deutlich verbesserte Lichtechtheit gegenüber sichtbarem und ultraviolettem Licht. Die Verbindungen der Formel (1) sind praktisch farblos, so dass es zu keiner Verfärbung der Bilder kommt; ausserdem sind sie gut verträglich mit den üblichen, in den einzelnen Schichten vorhandenen photographischen Zusatzstoffen; aufgrund ihrer guten Wirksamkeit kann man ihre Einsatzmenge herabsetzen und vermeidet so ihre Ausfällung oder ihr Auskristallisieren, wenn man sie als organische Lösung in die wässerigen Bindemittelemulsionen, die für die Herstellung photographischer Schichten verwendet werden, einarbeitet. Die einzelnen nach der Belichtung des photographischen Aufzeichnungsmaterials notwendigen Verarbeitungsschritte zur Herstellung der Farbbilder werden durch die Lichtschutzmittel nicht nachteilig beeinflusst. Ferner kann die bei blauempfindlichen Emulsionen häufig auftretende sogenannte Druckschleierbildung weitgehend zurückgedrängt werden. Diese kann z.B. auftreten, wenn auf photographische Materialien (Silberhalogenidemulsionsschichten, die sich auf einem Träger aus natürlichen oder synthetischen Materialien befinden) mechanische Beanspruchungen, z.B. Drehen, Biegen oder Reiben, während der Herstellung oder während der Behandlung vor der Entwicklung ausgeübt werden. (T.H. James, The Theory of the Photographic Process 4. Auflage, Macmillan, New York, N.Y. 1977, Seite 23 ff., S. 166 ff.)The color images obtained with the recording material according to the invention by exposure and development show a clearly improved light fastness to visible and ultraviolet light. The compounds of formula (1) are practically colorless, so that there is no discoloration of the images; in addition, they are well compatible with the usual photographic additives present in the individual layers; Because of their good effectiveness, their use amount can be reduced and thus their precipitation or crystallization is avoided if they are incorporated as an organic solution in the aqueous binder emulsions used for the production of photographic layers. The individual processing steps required to produce the color images after exposure of the photographic recording material are not adversely affected by the light stabilizers. Furthermore, the so-called pressure fog formation that frequently occurs with blue-sensitive emulsions can be largely suppressed. This can e.g. occur when mechanical stresses are exerted on photographic materials (silver halide emulsion layers supported on a support made of natural or synthetic materials), e.g. Rotate, bend or rub during manufacturing or during pre-development treatment. (T.H. James, The Theory of the Photographic Process 4th edition, Macmillan, New York, N.Y. 1977, page 23 ff., P. 166 ff.)

In den nachfolgenden Beispielen beziehen sich Teile und Prozente auf das Gewicht, sofern nichts anderes angegeben ist.In the examples below, parts and percentages are by weight unless otherwise specified.

Beispiel 1example 1

0,1 m Mol des Gelbkupplers der Formel

Figure imgb0034

und 0,04 mMol der Verbindung der Formel (3) [ferner der Verbindungen der Formeln (5), (7) und (23)] werden in 2,0 ml Trikresylphosphat/Aethylacetat (1:79) gelöst. Man gibt 7,0 ml 6%ige Gelatinelösung, 0,5 ml einer 8%igen Lösung des Netzmittels der Formel
Figure imgb0035
in Isopropanol/Wasser (3:4) und 0,5 ml Wasser hinzu, dann emulgiert man mit Hilfe eines Ultraschallgerätes und mit einer Leistung von 100 Watt, während 5 Minuten 2,5 ml frisch beschallte Kuppler-Additiv-Emulsion, 0,8 ml Silberbromidemulsion mit einem Gehalt von 2,8% Silber, 0,7 ml einer l%igen wässrigen Lösung der Härters der Formel
Figure imgb0036
0,4 ml 1,5 %ige wässrige Gelatinelösung und 4,0 ml Wasser werden miteinander vermischt, auf einen pH-Wert von 6,5 eingestellt und bei 40°C auf eine substrierte Glasplatte von Format 13x18 cm vergossen. Nach dem Erstarren der Schicht bei 10° C wird die Platte in einem Trockenschrank mit Umluft von Raumtemperatur getrocknet.0.1 m mol of the yellow coupler of the formula
Figure imgb0034
and 0.04 mmol of the compound of the formula (3) [further of the compounds of the formulas (5), (7) and (23)] are dissolved in 2.0 ml of tricresyl phosphate / ethyl acetate (1:79). 7.0 ml of 6% gelatin solution and 0.5 ml of an 8% solution of the wetting agent of the formula are added
Figure imgb0035
in isopropanol / water (3: 4) and 0.5 ml of water, then emulsified with the aid of an ultrasound device and with a power of 100 watts, for 5 minutes 2.5 ml of freshly sonicated coupler additive emulsion, 0.8 ml of silver bromide emulsion containing 2.8% silver, 0.7 ml of a 1% aqueous solution of the hardener of the formula
Figure imgb0036
0.4 ml of a 1.5% aqueous gelatin solution and 4.0 ml of water are mixed together, adjusted to a pH of 6.5 and poured onto a substrate glass plate of 13x18 cm format at 40 ° C. After the layer has solidified at 10 ° C., the plate is dried in a drying cabinet with circulating air at room temperature.

Verarbeitungprocessing

Ein auf ein Format von 4,0 cm x 6,5 cm geschnittener Streifen der beschichteten Glasplatte wird unter einem Stufenkeil während 6 Sekunden mit 500 Lux belichtet und anschliessend bei 32,8°C (± 0,3°C) wie folgt verarbeitet:

Figure imgb0037
A strip of the coated glass plate cut to a format of 4.0 cm x 6.5 cm is exposed to 500 lux for 6 seconds under a step wedge and then processed at 32.8 ° C (± 0.3 ° C) as follows:
Figure imgb0037

Das Entwicklerbad hat die folgende Zusammensetzung:

Figure imgb0038
The developer bath has the following composition:
Figure imgb0038

Der pH-Wert beträgt 10,1.The pH is 10.1.

Als Bleichfixierbad dient ein konventionelles Bad, das z.B. die folgende Zusammensetzung aufweist.

Figure imgb0039
A conventional bath, which has the following composition, for example, serves as the bleach-fix bath.
Figure imgb0039

Nach dem Wässern und Trocknen erhält man einen klaren, scharfen Gelbkeil mit einem Absorptionsmaximum bei 445 nm und einer Maximaldichte von 1,34.After washing and drying, a clear, sharp yellow wedge is obtained with an absorption maximum at 445 nm and a maximum density of 1.34.

Der so erhaltene Stufenkeil wird in einem Atlasgerät (Lampe 2500 W) mit jeweils 10'000 Langleyeinheiten mit und ohne Ultraviolettfilter (Kodakfilter 2C) bestrahlt.The step wedge obtained in this way is irradiated in an Atlas device (lamp 2500 W) with 10,000 Langley units each, with and without an ultraviolet filter (Kodak filter 2C).

Als Vergleich dienen jeweils ein analog hergestellter Stufenkeil, der kein Additiv enthält, sowie weitere Stufenkeile die unter Verwendung der Verbindungen der Formeln (104) und (107) bis (110) hergestellt wurden.A step wedge produced in an analog manner, which contains no additive, and further step wedges which were produced using the compounds of the formulas (104) and (107) to (110) are used for comparison.

Gemessen wird in allen Fällen die verbleibende optische Dichte (OD) in % der Anfangsdichte. Die Tabelle 1 enthält die Ergebnisse.In all cases, the remaining optical density (OD) is measured in% of the initial density. Table 1 contains the results.

Vergleichsverbindungen:

Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
(Beispiel 4 - DE-OS 2126954)
Figure imgb0044
(Beispiel 49 - DE-OS 2126187)
Figure imgb0045
Figure imgb0046
(Beispiel 34 - DE-OS 2126954)
Figure imgb0047
 Comparative compounds:
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
 (Example 4 - DE-OS 2126954)
Figure imgb0044
 (Example 49 - DE-OS 2126187)
Figure imgb0045
Figure imgb0046
 (Example 34 - DE-OS 2126954)
Figure imgb0047

Die Daten zeigen den guten Schutz des photographischen Materials gegen den schädlichen Einfluss von Licht, der bei Verwendung der erfindungsgemäss eingesetzten Lichtschutzmittel erreicht werden kann. Die Effekte sind deutlich verbessert im Vergleich zu denen, die mit bekanntenbereits in photographischen Materialien verwendeten Lichtschutzmitteln erreicht werden können. Mit den Verbindungen der Formeln (4), (6), (8) bis (22) und (24) bis (31) werden ebenfalls gute Ergebnisse erzielt.The data show the good protection of the photographic material against the harmful influence of light, which can be achieved when using the light stabilizers used according to the invention. The effects are significantly improved compared to those that can be achieved with known light stabilizers already used in photographic materials. Good results are also achieved with the compounds of the formulas (4), (6), (8) to (22) and (24) to (3 1 ).

Beispiel 2Example 2

0,4 m Mol des Cyankupplers der Formel

Figure imgb0048
und 0,02 mMol des Additives der Formel (5) [ferner der Additive der Formel (13) und (23)] werden in 2,0 ml Trikresylphosphat/Aethylacetat (1:159) gelöst. Man gibt 7,0 ml 6%iger Gelatinelösung, 0,5 ml einer 8%igen Lösung des Netzmittels der Formel (102) in Isopropanol/Wasser (3:4) und 0,5 ml Wasser hinzu; dann emulgiert man mit Hilfe eines Ultraschallgerätes mit einer Lösung von 100 Watt während 5 Minuten. 2,5 ml frisch beschallte Kuppler-Additiv-Emulsion, 0,4 ml Silberbromid-Emulsion mit einem Gehalt.von 2,8 % Silber , 0,7 ml einer 1 %igen Wässrigen Lösung des Härters der Formel (103),0.4 m mol of the cyan coupler of the formula
Figure imgb0048
 and 0.02 mmol of the additive of the formula (5) [further of the additive of the formula (13) and (23)] are dissolved in 2.0 ml of tricresyl phosphate / ethyl acetate (1: 159). 7.0 ml of 6% gelatin solution, 0.5 ml of an 8% solution of the wetting agent of the formula (102) in isopropanol / water (3: 4) and 0.5 ml of water are added; then emulsified with the aid of an ultrasound device with a solution of 100 watts for 5 minutes. 2.5 ml of freshly sonicated coupler additive emulsion, 0.4 ml of silver bromide emulsion containing 2.8% of silver, 0.7 ml of a 1% aqueous solution of the hardener of the formula (103),

0,4 ml '1,5 %ige wässrige Gelatinelösung und 4,0 ml Wasser werden miteinander vermischt, auf einen pH-Wert von 6,5 eingestellt und bei 40°C auf eine substrierte Glasplatte von Format 13 x 18 cm vergossen. Nach dem Erstarren der Schicht bei 10°C wird die Platte in einem Trockenschrank mit Umluft von Raumtemperatur getrocknet.0.4 ml of 1.5% aqueous gelatin solution and 4.0 ml of water are mixed with one another, adjusted to a pH of 6.5 and poured at 40 ° C. onto a 13 x 18 cm format glass plate. After the layer has solidified at 10 ° C., the plate is dried in a drying cabinet with ambient air at room temperature.

Verarbeitungprocessing

Ein auf ein Format von 4,0 cm x 6,5 cm geschnittener Streifen der beschichteten Glasplatte wird unter einem Stufenkeil während 6 Sekunden mit 500 Lux belichtet und anschliessend bei 32,8°C (± 0,3°C) wie in Beispiel 1 beschrieben verarbeitet.A strip of the coated glass plate cut to a format of 4.0 cm × 6.5 cm is exposed under a step wedge at 500 lux for 6 seconds and then at 32.8 ° C. (± 0.3 ° C.) as in Example 1 described processed.

Man erhält einen klaren, scharfen, blaugrün gefärbten Stufenkeil mit einem Absorptionsmaximum bei 653 nm und einer Maximaldichte von 1,10.A clear, sharp, blue-green colored step wedge is obtained with an absorption maximum at 653 nm and a maximum density of 1.10.

Der Stufenkeil sowie analog hergestellte Stufenkeile, die unter Verwendung der Verbindungen (105) bis (110) hergestellt wurden, werden wie in Beispiel 1 beschrieben belichtet und ausgemessen.Tabelle 2 enthält die Ergebnisse.

Figure imgb0049
The step wedge and step wedges produced analogously, which were produced using the compounds (105) to (110), are exposed and measured as described in Example 1. Table 2 contains the results.
Figure imgb0049

Mit den Verbindungen der Formeln (3), (4), (6) bis (12) (14) bis (22) und (24) bis (31) werden ebenfalls gute Ergebnisse erzielt.Good results are also obtained with the compounds of the formulas (3), (4), (6) to (12) (14) to (22) and (24) to (31).

Beispiel 3Example 3

3,5 10-3 Mol des GeJbkupplers der Formel

Figure imgb0050
(DE-OS 2716204) werden in 10 ml Essigsäureäthylester aufgelöst und mit 1,5 g Trikresylphosphat versetzt. Diese Lösung wird in 100 ml 4 %ige Gelatinelösung, welche 0,3 g eines Alkyl-aryl-sulfonat-Emulgators enthält, mit Hilfe eines Ultraschallgerätes emulgiert. Anschliessend wird der Essigsäureäthylester abdestilliert. Dieser Emulsion wird dann bei etwa 40° C eine lichtempfindliche Silberchloridbromiddispersion zugemischt (mittlere Partikelgrösse der Silberhalogenidkristalle etw 1µm) die in üblicher Weise chemisch sensibilisiert wurde.3.5 10 -3 moles of the GeJb coupler of the formula
Figure imgb0050
 (DE-OS 2716204) are dissolved in 10 ml of ethyl acetate and mixed with 1.5 g of tricresyl phosphate. This solution is emulsified in 100 ml of 4% gelatin solution, which contains 0.3 g of an alkyl aryl sulfonate emulsifier, using an ultrasound device. The ethyl acetate is then distilled off. This emulsion is then admixed with a light-sensitive silver chloride bromide dispersion (average particle size of the silver halide crystals about 1 μm) at about 40 ° C. which has been chemically sensitized in the usual way.

4m2 eines polyäthylenlaminierten Papierträgers werden mit dieser Mischung und anschliessend mit einer ein Härtungsmittel enthaltenden Gelatinelösung als Schutzschicht begossen. Man erhält so ein zweischichtiges photographisches Material an dem man die Druck- oder Biegeempfindlichkeit bestimmt. Dazu wird das getrocknete, photographische Material unter einer Zugspannung von etwa 1 kg über eine abgerundete Kante mit etwa 0,7 mm Krummungsradius in einen Winkel von ca. 90° gezogen. Diese Probe wird parallel mit einer Blindprobe durch einen Belichtungskeil belichtet, nach üblichen Verfahren verarbeitet und densitometrisch ausgewertet (Δ Dmin=sogenannter Druckschleier). Die Zunahme der Mini- maldichte im Vergleich zu der Blindprobe ist ein Mass für die Biegebeanspruchung.4m 2 of a polyethylene-laminated paper carrier are poured with this mixture and then with a gelatin solution containing a hardening agent as a protective layer. This gives a two-layer photographic material on which the sensitivity to pressure or bending is determined. To do this, the dried, photographic material is pulled together tension of about 1 kg over a rounded edge with about 0.7 mm radius of curvature at an angle of about 90 °. This sample is exposed in parallel with a blank sample through an exposure wedge, processed using conventional methods and evaluated densitometrically (Δ D min = so-called pressure fog). The increase in the minimum density compared to the blank is a measure of the bending stress.

Analog werden weitere photographische Materialien hergestellt, die zusätzlich zu dem Farbkuppler Lichtschutzmittel in Mengen von 0,7.10-3 Mol und 1,4·10-3 Mol pro m2 jeweils in Essigester aufgelöst, enthalten.Analog other photographic materials are prepared, each dissolved in addition to the color coupler ol light stabilizers in amounts of 0,7.10 -3 M and 1.4 x 10 -3 mol per m 2 in Essigester contain.

In der folgenden Tabelle 3 sind die dabei ermittelten Werte für den Druckschleier zusammengestellt.

Figure imgb0051
The values determined for the pressure curtain are summarized in Table 3 below.
Figure imgb0051

Beispiel 4Example 4

Man stellt Gelatinelösungen wie in Beispiel 1 her, verwendet jedoch die Lichtschutzmittel der Formeln (23) (erfindungsgemäss) und (105) und (106) (Vergleich) und den Gelbkuppler der Formel

Figure imgb0052
oder der Formel
Figure imgb0053
(DE-OS 2 757 380).Gelatin solutions are prepared as in Example 1, but the light stabilizers of the formulas (23) (according to the invention) and (105) and (106) (comparison) and the yellow coupler of the formula are used
Figure imgb0052
 or the formula
Figure imgb0053
 (DE-OS 2 757 380).

Die Lichtschutzmittel und die Gelbkuppler werden im molaren Verhältnis von 1 : 1 eingesetzt.The light stabilizers and the yellow couplers are used in a molar ratio of 1: 1.

Die Herstellung der beschichteten Glasplatten, die Belichtung und photographische Verarbeitung sowie der Lichtechtheitstest werden wie in Beispiel 1 ausgeführt. Der Lichtechtheitstest wird mit einer Bestrahlung von 15 000 Langleyeinheiten durchgeführt.The production of the coated glass plates, the exposure and photographic processing and the light fastness test are carried out as in Example 1. The light fastness test is carried out with an irradiation of 15,000 Langley units.

Gemessen wird in beiden Fällen die verbleibende optische Dichte (OD). Tabelle 4 enthält die Ergebnisse in % der Anfangsdichte. Es wird mit den erfindungsgemäss eingesetzten Verbindungen ein deutlich verbesserter Lichtschutz erreicht.

Figure imgb0054
In both cases, the remaining optical density (OD) is measured. Table 4 contains the results in% of the initial density. A significantly improved light protection is achieved with the compounds used according to the invention.
Figure imgb0054

Claims (8)

1. Farbphotographisches Aufzeichnungsmaterial, das in mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, einer Zwischenschicht und/oder einer Schutzschicht mindestens eine Piperidinverbindung als Lichtschutzmittel enthält, dadurch gekennzeichnet, dass die Piperidinverbindung der Formel
Figure imgb0055
entspricht, worin R1 Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen ist, R2 Alkyl oder Hydroxyalkyl mit je 1 bis 12 Kohlenstoffatomen, Alkenyl oder Alkinyl mit 3 oder 4 Kohlenstoffatomen, Benzyl oder R6CO- ist, worin R6 Wasserstoff, Alkyl mit 1 bis 12 Kohlenstoffatomen, Alkenyl mit 2 oder 3 Kohlenstoffatomen, Cyclohexyl, Benzyl oder gegebenenfalls mit zwei Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen und einer Hydroxylgruppe substituiertes Phenyl oder Phenyläthyl ist, R3 Wasserstoff oder Methyl ist, R4 und R5 je Alkyl mit 1 bis 5 Kohlenstoffatomen oder Cycloalkyl mit 5 bis 8 Kohlenstoffatomen sind, Y Wasserstoff, Alkyl mit 1 bis 12 Kohlenstoffatomen, -CnH2nC'OOR7, worin n 0 oder eine ganze Zahl von 1 bis 10 und R7 Wasserstoff, Alkyl mit 1 bis 18 Kohlenstoffatomen, bevorzugt Methyl oder Aethyl oder der Rest der Formel
Figure imgb0056
ist, oder Y CH2CH2CN, -NHCOR8 ist, worin R8 Methyl, Aethyl, Phenyl oder Benzyl ist, Y ferner Cyan, Benzyl oder der Rest der Formel
Figure imgb0057
worin R1 und R2 die angegebenen Bedeutungen haben, R9 Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen, m 1 oder 2 und p 1 oder 0 ist.1. Color photographic recording material which contains at least one piperidine compound as a light stabilizer in at least one light-sensitive silver halide emulsion layer, an intermediate layer and / or a protective layer, characterized in that the piperidine compound of the formula
Figure imgb0055
corresponds, in which R 1 is hydrogen or alkyl having 1 to 4 carbon atoms, R 2 is alkyl or hydroxyalkyl each having 1 to 12 carbon atoms, alkenyl or alkynyl having 3 or 4 carbon atoms, benzyl or R 6 CO-, in which R 6 is hydrogen, alkyl phenyl or phenylethyl substituted by 1 to 12 carbon atoms, alkenyl having 2 or 3 carbon atoms, cyclohexyl, benzyl or optionally substituted by two alkyl groups each having 1 to 4 carbon atoms and one hydroxyl group, R 3 is hydrogen or methyl, R 4 and R 5 are each alkyl with 1 to 5 carbon atoms or cycloalkyl with 5 to 8 carbon atoms, Y are hydrogen, alkyl with 1 to 12 carbon atoms, -C n H 2n C'OOR 7 , where n is 0 or an integer from 1 to 10 and R 7 is hydrogen, Alkyl having 1 to 18 carbon atoms, preferably methyl or ethyl or the rest of the formula
Figure imgb0056
or Y is CH 2 CH 2 CN, -NHCOR 8 , wherein R 8 is methyl, ethyl, phenyl or benzyl, Y is also cyan, benzyl or the rest of the formula
Figure imgb0057
wherein R 1 and R 2 have the meanings given, R 9 is hydrogen or alkyl having 1 to 4 carbon atoms, m 1 or 2 and p 1 or 0. 2. Farbphotographisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass die Piperidinverbindung der Formel
Figure imgb0058
entspricht, worin R10 Methyl, Aethyl, Benzyl, Acetyl, Acrylyl, Methacrylyl, Crotonyl, Allyl oder Propargyl ist.2. Color photographic recording material according to claim 1, characterized in that the piperidine compound of the formula
Figure imgb0058
corresponds in which R 10 is methyl, ethyl, benzyl, acetyl, acrylyl, methacrylyl, crotonyl, allyl or propargyl. 3. Farbphotographisches Aufzeichnungsmaterial nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass es die Lichtschutzmittel in Kombination mit Ultraviolettabsorbern enthält.3. Color photographic recording material according to one of claims 1 or 2, characterized in that it contains the light stabilizers in combination with ultraviolet absorbers. 4. Farbphotographisches Aufzeichnungsmaterial nach Anspruch 3, dadurch gekennzeichnet, dass die Ultraviolettabsorber Verbindungen von Benzophenon-, Acrylnitril-, Thiazolidon-, Benztriazol-, Oxazol-, Thiazol- oder Imidazoltyp sind.4. Color photographic recording material according to claim 3, characterized in that the ultraviolet absorbers are compounds of benzophenone, acrylonitrile, thiazolidone, benzotriazole, oxazole, thiazole or imidazole type. 5. Farbphotographisches Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es 1 bis 500 mg des Lichtschutzmittels und gegebenenfalls des Ultraviolettabsorbers pro m2 der Schicht enthält, in die es (sie) eingearbeitet ist (sind).5. Color photographic recording material according to one of claims 1 to 4, characterized in that it contains 1 to 500 mg of the light stabilizer and optionally of the ultraviolet absorber per m 2 of the layer into which it (it) is (are) incorporated. 6. Verfahren zur Stabilisierung von farbphotographischen Aufzeichnungsmaterialien, die mindestens eine lichtempfindliche Silberhalogenidemulsionsschicht enthalten, gegen die schädliche Einwirkung von Licht, dadurch gekennzeichnet, dass man in mindestens eine Silberhalogenidemulsionsschicht, eine Zwischenschicht und/oder eine Schutzschicht, 1 bis 500 mg pro m Schicht mindestens eines Lichtschutzmittels gemäss Anspruch 1, gegebenenfalls in Kombination mit Ultraviolettabsorbern einarbeitet.6. A method for stabilizing color photographic recording materials which contain at least one light-sensitive silver halide emulsion layer against the harmful effects of light, characterized in that 1 to 500 mg per m layer of at least one in at least one silver halide emulsion layer, an intermediate layer and / or a protective layer Light stabilizer according to claim 1, optionally incorporated in combination with ultraviolet absorbers. 7. Verfahren zur Herstellung von photographischen Farbbildern durch bildmässige Belichtung und Farbentwicklung eines farbphotographischen Aufzeichnungsmaterials gemäss einem der Ansprüche 1 bis 5.7. A process for the production of color photographic images by imagewise exposure and color development of a color photographic recording material according to one of claims 1 to 5. 8. Die gemäss dem Verfahren nach Anspruch 7 erhaltenen photographischen Farbbilder.8. The color photographic images obtained by the method of claim 7.
EP79810141A 1978-11-06 1979-10-31 Colour-photographic recording material, process for its stabilisation and production of colour-photographic images Expired EP0011051B1 (en)

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EP0103540A1 (en) * 1982-08-18 1984-03-21 Ciba-Geigy Ag Colour-photographic recording material
EP0109937A2 (en) * 1982-11-18 1984-05-30 Ciba-Geigy Ag Colour-photographic recording material
EP0110828A2 (en) * 1982-11-26 1984-06-13 Ciba-Geigy Ag Colour-photographic recording material
EP0111447A2 (en) * 1982-12-03 1984-06-20 Ciba-Geigy Ag Colour-photographic recording material
EP0111448A2 (en) * 1982-12-08 1984-06-20 Ciba-Geigy Ag Colour-photographic recording material
EP0112802A2 (en) * 1982-12-16 1984-07-04 Ciba-Geigy Ag Colour-photographic recording material
EP0113124A2 (en) * 1982-12-30 1984-07-11 Konica Corporation Silver halide photographic light-sensitive material
EP0114029A2 (en) * 1982-12-16 1984-07-25 Ciba-Geigy Ag Colour-photographic recording material
EP0114028A2 (en) * 1982-12-16 1984-07-25 Ciba-Geigy Ag Colour-photographic recording material
EP0104146B1 (en) * 1982-09-21 1986-07-30 Ciba-Geigy Ag Colour-photographic recording material

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EP0082817A1 (en) * 1981-12-17 1983-06-29 Ciba-Geigy Ag Colour-photographic recording material
EP0103540A1 (en) * 1982-08-18 1984-03-21 Ciba-Geigy Ag Colour-photographic recording material
EP0104146B1 (en) * 1982-09-21 1986-07-30 Ciba-Geigy Ag Colour-photographic recording material
EP0109937A2 (en) * 1982-11-18 1984-05-30 Ciba-Geigy Ag Colour-photographic recording material
EP0109937A3 (en) * 1982-11-18 1986-01-02 Ciba-Geigy Ag Colour-photographic recording material
EP0110828A2 (en) * 1982-11-26 1984-06-13 Ciba-Geigy Ag Colour-photographic recording material
EP0110828A3 (en) * 1982-11-26 1985-12-27 Ciba-Geigy Ag Colour-photographic recording material
EP0111447A2 (en) * 1982-12-03 1984-06-20 Ciba-Geigy Ag Colour-photographic recording material
EP0111447A3 (en) * 1982-12-03 1986-01-02 Ciba-Geigy Ag Colour-photographic recording material
EP0111448A3 (en) * 1982-12-08 1985-12-27 Ciba-Geigy Ag Colour-photographic recording material
EP0111448A2 (en) * 1982-12-08 1984-06-20 Ciba-Geigy Ag Colour-photographic recording material
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EP0114028A3 (en) * 1982-12-16 1985-12-27 Ciba-Geigy Ag Colour-photographic recording material
EP0114029A3 (en) * 1982-12-16 1985-12-27 Ciba-Geigy Ag Colour-photographic recording material
EP0112802A3 (en) * 1982-12-16 1985-12-11 Ciba-Geigy Ag Colour-photographic recording material
EP0114028A2 (en) * 1982-12-16 1984-07-25 Ciba-Geigy Ag Colour-photographic recording material
EP0114029A2 (en) * 1982-12-16 1984-07-25 Ciba-Geigy Ag Colour-photographic recording material
EP0112802A2 (en) * 1982-12-16 1984-07-04 Ciba-Geigy Ag Colour-photographic recording material
EP0113124A3 (en) * 1982-12-30 1985-10-23 Konishiroku Photo Industry Co. Ltd. Silver halide photographic light-sensitive material
EP0113124A2 (en) * 1982-12-30 1984-07-11 Konica Corporation Silver halide photographic light-sensitive material

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