EP0114028B1 - Colour-photographic recording material - Google Patents

Colour-photographic recording material Download PDF

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Publication number
EP0114028B1
EP0114028B1 EP83810582A EP83810582A EP0114028B1 EP 0114028 B1 EP0114028 B1 EP 0114028B1 EP 83810582 A EP83810582 A EP 83810582A EP 83810582 A EP83810582 A EP 83810582A EP 0114028 B1 EP0114028 B1 EP 0114028B1
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EP
European Patent Office
Prior art keywords
alkyl
tert
butyl
formula
group
Prior art date
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Expired
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EP83810582A
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German (de)
French (fr)
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EP0114028A2 (en
EP0114028A3 (en
Inventor
David G. Dr. Leppard
Jean Dr. Rody
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Novartis AG
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Ciba Geigy AG
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Publication of EP0114028A2 publication Critical patent/EP0114028A2/en
Publication of EP0114028A3 publication Critical patent/EP0114028A3/en
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C7/39296—Combination of additives
    • 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
    • G03C7/39212—Carbocyclic
    • G03C7/39216—Carbocyclic with OH groups
    • 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
    • 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
    • G03C7/39256—Heterocyclic the nucleus containing only nitrogen as hetero atoms three nitrogen atoms
    • 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
    • G03C7/3928—Spiro-condensed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/132—Anti-ultraviolet fading
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/162—Protective or antiabrasion layer

Definitions

  • the present application relates to a color photographic recording material which contains, in at least one light-sensitive silver halide emulsion layer and / or in at least one of the customary auxiliary layers for stabilization, a mixture of a polyalkylpiperidine light stabilizer specifically substituted on the piperidine nitrogen and a phenolic antioxidant.
  • a polyalkylpiperidine light stabilizer specifically substituted on the piperidine nitrogen and a phenolic antioxidant.
  • polyalkylpiperidines are generally known as light stabilizers for organic materials, in particular for polymers.
  • FR-A-2 357 559 describes the possibility of using polyalkylpiperidines, if appropriate together with antioxidants, for stabilizing polymers.
  • Polyalkylpiperidine compounds preferred as component i) are those in which in the group of the formula I, R 1 allyl, benzyl, one group b is one of the numbers 0 or 2, R 7 is C 1 -C 4 alkyl, allyl or benzyl, R 8 is C 1 -C 4 alkyl, allyl or cyclohexyl, Rg is C 1 -C 12 alkyl or allyl or R 8 and Rg together with the N atom to which they are attached form a morpholine or piperidine residue and R io C 1 -C 12 alkyl, vinyl, cyclohexyl, benzyl or phenyl, R 11 hydrogen, methyl or phenyl and R 12 hydrogen, methyl or one Group -CON (R 8 ) (R 9 ) where R 8 and R 9 have the meaning already given in this preference.
  • R 14 is a monovalent radical of a carboxylic acid, it is, for example, an acetic, stearic, salicylic, methacrylic, benzoic or ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid residue .
  • R 14 is a divalent radical of a dicarboxylic acid, it is, for example, a maleic, adipic, suberic, sebacic, phthalic, dibutylmalonic, dibenzylmalonic or butyl (3,5-di-tert-butyl-4) -hydroxybenzyl) -malonic acid residue.
  • R 14 represents a trivalent radical of a tricarboxylic acid, it means z.
  • R 14 is a divalent radical of a dicarbamic acid, it represents, for example, a hexamethylene-dicarbamic acid or a 2,4-tolylene-dicarbamic acid radical.
  • polyalkylpiperidine compounds of this class are listed in Table I below.
  • any substituents are C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl or C 2 -C 12 alkylene, they have the meaning already given under a).
  • R 16 is a C 2 -C 8 alkenyl optionally substituted with a cyano, carbonyl or carbamide group, then it is, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2- Octenyl, 2,2-dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonyl-vinyl, 2,2-diacetylaminovinyl.
  • Any C 6 -C 15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  • X is in particular cyclohexylene.
  • polyalkylpiperidine compounds of this class are listed in Table II below.
  • R 17 is hydrogen, C 1 -C 12 alkyl, a group -CH 2 -OCOR 22 , wherein R 22 is hydrogen, C 1 -C 4 alkyl, C 2 -C 6 alkenyl, cyclohexyl, phenyl, benzyl or chloromethyl is a group -CH 2 O-S (O) qR 23 , wherein R 23 is C 1 -C 4 alkyl, p-tolyl or phenyl and q represents the numbers 1 or 2, where R 17 represents a group -CH 2 OCO -NHR 24 means wherein R 24 is hydrogen or C 1 -C 4 alkyl, R 18 is hydrogen or C 1 -C 4 alkyl, R 19 is hydrogen, C 1 -C 12 alkyl, C 3 -C 4 alkoxyalkyl, C 5 -C 8 denotes cycloalkyl, allyl or benzyl, R 20 denotes hydrogen, C 1 -C 4 alkyl,
  • C 5 -C 12 cycloalkylene R 25 means z.
  • B cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene or cyclododecylene. Cyclohexylene is preferred.
  • Y is C 1 -C 18 alkyl z.
  • B methyl, ethyl, propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, 2,3-dimethylbutyl, n-octyl, 1, 1,3,3-tetramethylbutyl, nonyl, decyl, dodecyl, hexadecyl or octadecyl.
  • YC 2 -C 12 alkanoyl it is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.
  • polyalkylpiperidine compounds of this class are the following compounds 18 and 19
  • R 28 is a group of the formula means in which R and R 1 have the meaning given for formula I, QO- or -N (R 31 ) -, AC 2 -C 6 alkylene and m are the numbers 0 or 1
  • R 29 is the groups R 28
  • NR 31 is R 32 , -OR 33 , -NHCH 2 0R 33 or -N (CH 2 OR 33 ) 2
  • R 31 is hydrogen, C 1 -C 12 alkyl, allyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl or a group of the formula R 32 is C 1 -C 12 alkyl, allyl, cyclohexyl, benzyl or C 1 -C 4 hydroxy
  • R 31 and R 32 are C 1 -C 4 hydroxyalkyl, they are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • a or DC is 2 -C 6 alkylene, they are, for example, ethylene, propylene, 2,2-dimethyl propylene, tetramethylene or hexamethylene.
  • R 31 and R 32 together represent C4-C5 alkylene or oxaalkylene, this means, for. B. tetramethylene, pentamethylene or 3-oxapentamethylene.
  • polyalkylpiperidine compounds of this class are listed in Table IV below:
  • any substituents are C 1 -C 12 alkyl, they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Any substituents which are C 1 -C 18 alkyl can represent, for example, the groups mentioned above and, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • any groups C2-C10 represent alkylene, they mean, for example, ethylene, propylene, 2,2-dimethyl-propylene, tetramethylene, hexamethylene, octamethylene or decamethylene.
  • R 35 as C 4 -C 18 alkyl z.
  • B n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n - decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • R 35 is a C 1 -C 4 alkyl substituted by-CN, it is, for example, cyanomethyl, cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl.
  • R 35 is C4-C12 alkylene, it is, for example, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • R 35 is C 7 -C 12 aralkyl, it means in particular phenylethyl, p-methyl-benzyl or especially benzyl.
  • R 36 as C 2 -C 4 alkenyl means, for example, vinyl, 1-propenyl, allyl, methallyl, 2-butenyl.
  • R 38 means, for example, the groups mentioned for R 36 as alkenyl and, for example, crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.
  • R 38 is C 6 -C 10 aryl, it means, for example, phenyl which is unsubstituted or substituted in the o- or p-position by methyl, ethyl, isopropyl, n-butyl or tert-butyl.
  • polymeric compounds selected from the group consisting of polyester, polyether, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and their copolymers, the recurring structural units of which contain a group of formula 1 or are connected via a bivalent group corresponding to formula (I), in which R 1 is a free valence, where R and R 1 have the meaning given for formula I.
  • polyalkylpiperidine compounds of this class are the compounds of the following formulas, where m denotes the numbers 2 to about 200.
  • polyalkylpiperidine compounds to be used as component i) according to the invention are generally known.
  • the stabilizer mixture according to the invention can be incorporated into a photographic material alone or together with other compounds in a known manner.
  • the mixing ratio of the polyalkylpiperidine light stabilizer i) to the phenolic antioxidant ii) varies, for example, between 90:10 and 10:90, preferably between 70:30 and 30:70.
  • the stabilizer mixture is incorporated into the photographic material in the form of a dispersion, this dispersion either containing no solvent or high or low-boiling solvent or a mixture of such solvents.
  • Another suitable form of incorporation is that the stabilizers are incorporated into the photographic material alone or together with other compounds together with a polymer in the form of a latex.
  • the dispersions are then used to produce the layers of color photographic recording materials.
  • These layers can e.g. B. Intermediate or protective layers, but especially photosensitive (blue, green and red sensitive) silver halide emulsion layers, in which in the development of the exposed recording material from the corresponding color couplers, the cyan (cyan) -, magenta (magenta) - and Yellow dyes are formed.
  • the silver halide layers can contain any desired color couplers, in particular cyan, magenta and yellow couplers, which are used to form the dyes mentioned and thus the color formers.
  • substrates solvents, polymers
  • solvents, polymers are preferred which, together with the stabilizers, give the materials to be stabilized as good a resistance as possible.
  • the stabilizer mixtures are incorporated in layers which additionally contain a silver halide dispersion which has been prepared and sensitized by customary methods. However, they can also be present in layers adjacent to layers containing silver halide.
  • the photographic materials according to the invention have a customary structure and components which enhance the effectiveness of the stabilizer mixtures or at least do not adversely affect them.
  • the stabilizer mixtures containing components i) and ii) can also be combined with ultraviolet absorbers or other light stabilizers in the same layer in addition to the color couplers.
  • the stabilizer mixture can also be incorporated into a receiving layer.
  • the color photographic materials according to the invention can be processed in a known manner be tested. Furthermore, they can be treated in the course or after processing in a manner which further increases their stability, for example by treatment in a stabilizer bath or the application of a protective coating.
  • the invention further relates to a process for the production of color photographic images by imagewise exposure and color development of a color photographic recording material containing a stabilizer mixture with components i) and ii).
  • the invention further relates to the photographic color images obtained by this process.
  • the stabilizer mixtures to be used according to the invention are also suitable for protecting color photographic layers in which the dyes are incorporated directly into the emulsion and the image is produced by selective bleaching.
  • the amount of stabilizer mixture can vary within wide limits and is approximately in the range from 1 to 2000 mg, preferably 100 to 800 and in particular 200 to 500 mg per m 2 of the layer into which it is incorporated.
  • the photographic material contains one or more UV absorbers, this can be present together with the stabilizer mixture in one layer or in an adjacent layer.
  • the amount of UV absorber can vary within wide limits and is approximately in the range of 200-2000 mg, preferably 400-1000 mg per m 2 of the layer.
  • suitable UV absorbers are those of the benzophenone, acrylonitrile, thiazolidone, benzotriazole, oxazole, thiazole and imidazole type.
  • the color images obtained by exposure and development with the recording material according to the invention show very good light fastness to visible and ultraviolet light.
  • the stabilizer mixtures i) + ii) 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 their precipitation or crystallization can be 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 stabilizer mixtures i) + ii).
  • drying is carried out in a drying cabinet with circulating air at room temperature.
  • the yellow wedges obtained in this way are irradiated in an Atlas Weather-Ometer with a 2500 W xenon lamp with a total of 42 kJoules / cm 2 (a comparative sample contains no light stabilizer).
  • Table 1 shows the percentage decreases in yellow density with an original reflectance density of 1.0 in blue.
  • Table 2 contains the corresponding density decreases.
  • Table 3 contains the percentage density decreases obtained at the maximum with an initial reflectance density of 1.0.

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

Description

Die vorliegende Anmeldung betrifft ein farbphotographisches Aufzeichnungsmaterial, das in mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht und/oder in mindestens einer der üblichen Hilfsschichten zur Stabilisierung ein Gemisch aus einem spezifisch am Piperidinstickstoff substituierten Polyalkylpiperidin-Lichtschutzmittel und einem phenolischen Antioxidans enthält. Polyalkylpiperidine sind als sterisch gehinderte Amine allgemein als Lichtschutzmittel für organische Materialien, insbesondere für Polymere, bekannt. So beschreibt zum Beispiel die FR-A-2 357 559 die Möglichkeit, Polyalkylpiperidine gegebenenfalls zusammen mit Antioxidantien zur Stabilisierung von Polymeren einzusetzen. Es wurde auch bereits in der DE-OS 2 126 954 vorgeschlagen, solche Polyalkylpiperidine als Mittel gegen das Ausbleichen von Farbphotographien zu verwenden. Es wurde weiterhin in der EP-A-11 051 vorgeschlagen, als Lichtschutzmittel für Farbphotographien bestimmte Polyalkylpiperidinderivate zu verwenden, die mindestens eine Phenolgruppe enthalten. Es handelt sich dabei um Polyalkylpiperidinester von Hydroxylbenzylmalonsäuren.The present application relates to a color photographic recording material which contains, in at least one light-sensitive silver halide emulsion layer and / or in at least one of the customary auxiliary layers for stabilization, a mixture of a polyalkylpiperidine light stabilizer specifically substituted on the piperidine nitrogen and a phenolic antioxidant. As sterically hindered amines, polyalkylpiperidines are generally known as light stabilizers for organic materials, in particular for polymers. For example, FR-A-2 357 559 describes the possibility of using polyalkylpiperidines, if appropriate together with antioxidants, for stabilizing polymers. It has also already been proposed in DE-OS 2 126 954 to use such polyalkylpiperidines as agents against the fading of color photographs. It was further proposed in EP-A-11 051 to use certain polyalkylpiperidine derivatives which contain at least one phenol group as light stabilizers for color photographs. These are polyalkylpiperidine esters of hydroxylbenzylmalonic acids.

Es ist nun gefunden worden, dass Gemische aus spezifisch am Piperidinstickstoff substituierten Polyalkylpiperidin-Lichtschutzmitteln und phenolischen Antioxidantien eine überraschend bessere stabilisierende Wirkung ausüben.It has now been found that mixtures of polyalkylpiperidine light stabilizers specifically substituted on the piperidine nitrogen and phenolic antioxidants have a surprisingly better stabilizing effect.

Gegenstand der vorliegenden Erfindung ist daher ein farbphotographisches Aufzeichnungsmaterial, das in mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, einer Zwischenschicht und/oder einer Schutzschicht ein Stabilisatorgemisch enthaltend

  • i) eine Verbindung, die mindestens eine Gruppe der Formel I
    Figure imgb0001
    enthält, oder ein Polymer, dessen wiederkehrende Struktureinheiten eine Gruppe der Formel I enthalten oder über eine bivalente Gruppe entsprechend der Formel worin R1 eine freie Valenz bedeutet, verbunden sind, wobei im übrigen R Wasserstoff oder Methyl und R1 Methyl, eine Gruppe -CH2-C(R2) = C(R3)(R4),
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
    a und b eine der Zahlen 0, 1 oder 2, R2, R3 und R4 unabhängig voneinander Wasserstoff oder C1-C3 Alkyl, R5 Wasserstoff oder Methyl, R6 C1-C4 Alkyl, R7 C1-C12 Alkyl, Allyl, Benzyl oder Cyclohexyl, RB C1-C12 Alkyl, Allyl, Cyclohexyl, Benzyl oder Phenyl, Rg Wasserstoff, C1-C12 Alkyl, Allyl bedeuten oder R8 und Rg zusammen mit dem N-Atom an das sie gebunden sind einen 5- oder 6-gliedrigen heterocyclischen Ring bilden, und R10 Wasserstoff, C4-C12 Alkyl, C2-C6 Alkenyl, Chlormethyl, C5-C8 Cycloalkyl, C7-C14 Aralkyl, C7-C10 Alkylphenyl, R11 Wasserstoff, C1-C4 Alkyl, C2-C13 Alkoxymethyl, Phenyl oder Phenoxymethyl, R12 Wasserstoff, C1-C12 Alkyl, -COR10 oder -CON(R8)(R9), wobei R8, Rg und R10 die oben angegebene Bedeutung haben, und R13 C1-C12 Alkyl, Phenyl oder C7-C14 Alkaryl bedeuten, und
  • ii) ein phenolisches Antioxidans enthält.
The present invention therefore relates to a color photographic recording material which contains a stabilizer mixture in at least one light-sensitive silver halide emulsion layer, an intermediate layer and / or a protective layer
  • i) a compound which contains at least one group of the formula I.
    Figure imgb0001
     contains, or a polymer, the recurring structural units of which contain a group of the formula I or are connected via a bivalent group corresponding to the formula in which R 1 is a free valence, where R is hydrogen or methyl and R 1 is methyl, a group -CH 2 -C (R 2 ) = C (R 3 ) (R 4 ),
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
     a and b one of the numbers 0, 1 or 2, R 2 , R 3 and R 4 independently of one another hydrogen or C 1 -C 3 alkyl, R 5 hydrogen or methyl, R 6 C 1 -C 4 alkyl, R 7 C 1 -C 12 alkyl, allyl, benzyl or cyclohexyl, R B is C 1 -C 12 alkyl, allyl, cyclohexyl, benzyl or phenyl, Rg is hydrogen, C 1 -C 12 alkyl, allyl or R 8 and Rg together with the N - Atoms to which they are attached form a 5- or 6-membered heterocyclic ring, and R 10 is hydrogen, C 4 -C 12 alkyl, C 2 -C 6 alkenyl, chloromethyl, C 5 -C 8 cycloalkyl, C 7 -C 14 Aralkyl, C 7 -C 10 alkylphenyl, R 11 hydrogen, C 1 -C 4 alkyl, C 2 -C 13 alkoxymethyl, phenyl or phenoxymethyl, R 12 hydrogen, C 1 -C 12 alkyl, -COR 10 or -CON (R 8 ) (R 9 ), where R 8 , Rg and R 10 have the meaning given above, and R 13 is C 1 -C 12 alkyl, phenyl or C 7 -C 14 alkaryl, and
  • ii) contains a phenolic antioxidant.

Als Komponente i) bevorzugte Polyalkylpiperidinverbindungen sind solche, bei denen in der Gruppe der Formel I, R1 Allyl, Benzyl, eine Gruppe

Figure imgb0007
Figure imgb0008
b eine der Zahlen 0, oder 2, R7 C1-C4 Alkyl, Allyl oder Benzyl, R8 C1-C4 Alkyl, Allyl oder Cyclohexyl, Rg C1-C12 Alkyl oder Allyl bedeuten oder R8 und Rg zusammen mit dem N-Atom an das sie gebunden sind einen Morpholin- oder Piperidinrest bilden und Rio C1-C12 Alkyl, Vinyl, Cyclohexyl, Benzyl oder Phenyl, R11 Wasserstoff, Methyl oder Phenyl und R12 Wasserstoff, Methyl oder eine Gruppe -CON(R8)(R9) wobei R8 und R9 die in dieser Bevorzugung bereits gegebene Bedeutung haben, bedeuten.Polyalkylpiperidine compounds preferred as component i) are those in which in the group of the formula I, R 1 allyl, benzyl, one group
Figure imgb0007
Figure imgb0008
 b is one of the numbers 0 or 2, R 7 is C 1 -C 4 alkyl, allyl or benzyl, R 8 is C 1 -C 4 alkyl, allyl or cyclohexyl, Rg is C 1 -C 12 alkyl or allyl or R 8 and Rg together with the N atom to which they are attached form a morpholine or piperidine residue and R io C 1 -C 12 alkyl, vinyl, cyclohexyl, benzyl or phenyl, R 11 hydrogen, methyl or phenyl and R 12 hydrogen, methyl or one Group -CON (R 8 ) (R 9 ) where R 8 and R 9 have the meaning already given in this preference.

Zu den erfindungsgemäss als Komponente i) zu verwendenden Polyalkylpiperidinverbindungen gehören insbesondere folgende Verbindungsklassen

  • a) Verbindungen der Formel II
    Figure imgb0009
    worin n die Zahlen 1 bis 4 bedeutet, R und R1 die für Formel I angegebene Bedeutung haben und R14 wenn n = 1, Wasserstoff, C1-C12 Alkyl, Cyanethyl, Benzyl, Glycidyl, einen einwertigen Rest einer gesättigten oder ungesättigten aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Carbonsäure, Carbaminsäure oder Phosphor enthaltenden Säure oder einen einwertigen Silylrest, wenn n = 2, C2-C12 Alkylen, C4-C8 Alkenylen, Xylylen, einen zweiwertigen Rest einer gesättigten oder ungesättigten aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Dicarbonsäure, Dicarbaminsäure oder Phosphor enthaltenden Säure oder einen zweiwertigen Silylrest, wenn n = 3, einen dreiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tricarbonsäure, einer aromatischen Tricarbaminsäure oder einer Phosphor enthaltenden Säure oder einen dreiwertigen Silylrest, wenn n = 4, einen vierwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tetracarbonsäure bedeutet.
The polyalkylpiperidine compounds to be used according to the invention as component i) include in particular the following classes of compounds
  • a) Compounds of formula II
    Figure imgb0009
     wherein n is the numbers 1 to 4, R and R 1 have the meaning given for formula I and R 14 when n = 1, hydrogen, C 1 -C 12 alkyl, cyanoethyl, benzyl, glycidyl, a monovalent radical of a saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical if n = 2, C 2 -C 12 alkylene, C 4 -C 8 alkenylene, xylylene, a divalent radical of a saturated or unsaturated aliphatic, cycloaliphatic , araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical if n = 3, a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl residue, if n = 4, is a tetravalent residue of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

Bedeuten etwaige Substituenten Alkyl, so handelt es sich um geradkettige oder verzweigte Alkylgruppen. Bedeuten sie Cl-C4 Alkyl, dann handelt es sich um Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sec.-Butyl oder tert.-Butyl. Bedeuten sie C1-C8 Alkyl, so kommen zusätzlich z.B. n-Pentyl, 2,2-Dimethylpropyl, n-Hexyl, 2,3-Dimethylbutyl, n-Octyl oder 1,1,3,3-Tetramethylbutyl in Frage. Bedeuten sie C1-C12 Alkyl, so können sie zusätzlich auch z.B. Nonyl, Decyl, Undecyl oder Dodecyl sein. R2, R3 und R4 bedeuten als Ci-C3 Alkyl, Methyl, Ethyl, n-Propyl und Isopropyl. Bevorzugt ist Methyl.

  • R10 bedeutet als C5-C8 Cycloalkyl z.B. Cyclopentyl, Cyclohexyl, Cycloheptyl, a-Methylcyclohexyl, Cyclooctyl oder Dimethylcyclohexyl. Bevorzugt ist Cyclohexyl.
  • R10 ist als C2-C6Alkenyl z.B. Vinyl, Allyl, Methallyl, Dimethylallyl oder 2-Hexenyl. Bevorzugt ist Vinyl.
If any substituents are alkyl, they are straight-chain or branched alkyl groups. If they are C 1 -C 4 alkyl, then it is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl. If they are C 1 -C 8 alkyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, 2,3-dimethylbutyl, n-octyl or 1,1,3,3-tetramethylbutyl are also suitable. If they are C 1 -C 12 alkyl, they can also be, for example, nonyl, decyl, undecyl or dodecyl. R 2 , R 3 and R 4 mean as C 1 -C 3 alkyl, methyl, ethyl, n-propyl and isopropyl. Methyl is preferred.
  • R 10 as C 5 -C 8 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, a-methylcyclohexyl, cyclooctyl or dimethylcyclohexyl. Cyclohexyl is preferred.
  • R 10 is as C 2 -C 6 alkenyl, for example vinyl, allyl, methallyl, dimethylallyl or 2-hexenyl. Vinyl is preferred.

Bedeutet R10 C7-C14 Aralkyl, so handelt es sich z.B. um Benzyl, Phenylethyl, Phenylpropyl, Phenylbutyl oder Naphthylmethyl. Bevorzugt ist Benzyl.

  • R10 ist als C7-C10 Alkylphenyl beispielsweise Tolyl, Xylyl, Isopropylphenyl, tert.-Butylphenyl oder Diethylphenyl.
  • R11 ist als C2-C13 Alkoxymethyl z. B. Methoxy-, Ethoxy-, Propoxy-, Isopropoxy-, Butoxy-, Pentyloxy-, Hexyloxy-, Octyloxy-, Decyloxy- oder Dodecyloxymethyl.
  • R13 bedeutet als C7-C14 Alkaryl beispielsweise durch C1-C4 Alkyl substituiertes Phenyl, wie p-Tolyl, 2,4-Dimethylphenyl, 2,6-Dimethylphenyl, 2,4-Diethylphenyl, 2,6-Diethylphenyl, 4-tert.-Butylphenyl, 2,4-Di-tert.-butylphenyl oder 2,6-Di-tert.-butylphenyl. Bevorzugt sind 2,4-Di-tert.-butylphenyl, 2,4-Dimethylphenyl und p-Tolyl.
  • R14 kann als C2-C12 Alkylen z.B. Ethylen, Propylen, 2,2-Dimethylpropylen, Tetramethylen, Hexamethylen, Octamethylen, Decamethylen oder Dodecamethylen sein.
If R 10 is C 7 -C 14 aralkyl, it is, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl or naphthylmethyl. Benzyl is preferred.
  • R 10 as C 7 -C 10 alkylphenyl is, for example, tolyl, xylyl, isopropylphenyl, tert-butylphenyl or diethylphenyl.
  • R 11 is as C 2 -C 13 alkoxymethyl z. B. methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy or dodecyloxymethyl.
  • R 13 as C 7 -C 14 alkaryl is, for example, phenyl substituted by C 1 -C 4 alkyl, such as p-tolyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 4-tert-butylphenyl, 2,4-di-tert-butylphenyl or 2,6-di-tert-butylphenyl. 2,4-Di-tert-butylphenyl, 2,4-dimethylphenyl and p-tolyl are preferred.
  • R 14 can be as C 2 -C 12 alkylene, for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Als C4-C8 Alkenylen bedeutet R14 z. B. 2-Butenylen-1,4.As C 4 -C 8 alkenylene R 14 means z. B. 2-butenylene-1,4.

Bedeutet R14 einen einwertigen Rest einer Carbonsäure, so stellt es beispielsweise einen Essigsäure-, Stearinsäure-, Salicylsäure-, Methacrylsäure-, Benzoe- oder ß-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-propionsäurerest dar.If R 14 is a monovalent radical of a carboxylic acid, it is, for example, an acetic, stearic, salicylic, methacrylic, benzoic or ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid residue .

Bedeutet R14 einen zweiwertigen Rest einer Dicarbonsäure, so stellt es beispielsweise einen Maleinsäure-, Adipinsäure-, Suberinsäure-, Sebacinsäure-, Phthalsäure-, Dibutylmalonsäure-, Dibenzylmalonsäure- oder Butyl-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonsäurerest dar.If R 14 is a divalent radical of a dicarboxylic acid, it is, for example, a maleic, adipic, suberic, sebacic, phthalic, dibutylmalonic, dibenzylmalonic or butyl (3,5-di-tert-butyl-4) -hydroxybenzyl) -malonic acid residue.

Stellt R14 einen dreiwertigen Rest einer Tricarbonsäure dar, so bedeutet es z. B. einen Pyromellithsäurerest.R 14 represents a trivalent radical of a tricarboxylic acid, it means z. B. a pyromellitic acid residue.

Bedeutet R14 einen zweiwertigen Rest einer Dicarbaminsäure, so stellt es beispielsweise einen Hexamethylen-dicarbaminsäure- oder einen 2,4-Toluylen-dicarbaminsäurerest dar.If R 14 is a divalent radical of a dicarbamic acid, it represents, for example, a hexamethylene-dicarbamic acid or a 2,4-tolylene-dicarbamic acid radical.

Besonders interessant sind Verbindungen der Formel II, worin n die Zahlen 1 oder 2 bedeutet und Ri4 wenn n = 1 einen Rest einer aliphatischen Carbonsäure mit 2-18 C-Atomen, einer cycloaliphatischen Carbonsäure mit 5-12 C-Atomen oder einer aromatischen Carbonsäure mit 7-15 C-Atomen, wenn n = 2 einen Rest einer aliphatischen Dicarbonsäure mit 2-12 C-Atomen, einer cycloaliphatischen oder aromatischen Dicarbonsäure mit 8-14 C-Atomen, einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbaminsäure mit 8-14 C-Atomen bedeutet.Of particular interest are compounds of the formula II in which n is the number 1 or 2 and R i4 when n = 1 is a radical of an aliphatic carboxylic acid having 2-18 C atoms, a cycloaliphatic carboxylic acid having 5-12 C atoms or an aromatic carboxylic acid with 7-15 C atoms, if n = 2 a residue of an aliphatic dicarboxylic acid with 2-12 C atoms, a cycloaliphatic or aromatic dicarboxylic acid with 8-14 C atoms, an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8-14 C -Atoms means.

Beispiele für Polyalkylpiperidinverbindungen dieser Klasse sind in der nachfolgenden Tabelle I aufgeführt.

Figure imgb0010
Examples of polyalkylpiperidine compounds of this class are listed in Table I below.
Figure imgb0010

Weitere Beispiele für Verbindungen dieser Klasse, nämlich von Verbindungen der Formel II, worin n = 4 ist, sind die folgenden Verbindungen 5 und 6

Figure imgb0011
Further examples of compounds of this class, namely compounds of the formula II in which n = 4, are the following compounds 5 and 6
Figure imgb0011

b) Verbindungen der Formel III

Figure imgb0012
worin c.die Zahlen 1 oder 2 bedeutet, und R und R1 die für Formel I angegebene Bedeutung haben, R15 C1-C12 Alkyl, C5-C8 Cycloalkyl, C7-C8 Aralkyl, C2-C18 Alkanoyl oder Benzoyl ist und R16, wenn c = 1, C1-C12 Alkyl, C5-C8 Cycloalkyl, unsubstituiertes oder durch eine Cyano-, Carbonyl- oder Carbamidgruppe substituiertes C2-C8 Alkenyl, Glycidyl, eine Gruppe der Formeln -CHz-CH(OH)-Z, -COO-Z oder -CONH-Z ist, worin Z Wasserstoff, Methyl oder Phenyl bedeutet, und, wenn c = 2, CZ-C12 Alkylen, C6-C12 Arylen, Xylylen, eine -CH2-CH(OH)-CH2-Gruppe oder eine Gruppe -CH2-CH(OH)-CH2-O-X-O-CH2-CH(OH)-CH2- bedeutet, worin X C2-C10 Alkylen, C6-C15 Arylen oder C6-C12 Cycloalkylen ist, oder, vorausgesetzt, dass R15 nicht Alkanoyl, Alkenoyl oder Benzoyl bedeutet, R16 auch einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure oder Dicarbaminsäure bedeuten kann, oder R15 und R16 zusammen, wenn c = 1, den cyclischen Rest einer aliphatischen oder aromatischen 1,2- oder 1,3-Dicarbonsäure sein können.b) compounds of the formula III
Figure imgb0012
 wherein c. the numbers 1 or 2, and R and R 1 have the meaning given for formula I, R 15 C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 18 is alkanoyl or benzoyl and R 16 when c = 1, C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl, unsubstituted or substituted by a cyano, carbonyl or carbamide group, C 2 -C 8 alkenyl, glycidyl, a Group of the formulas -CH z -CH (OH) -Z, -COO-Z or -CONH-Z, in which Z is hydrogen, methyl or phenyl, and, if c = 2, C Z -C 12 alkylene, C 6 -C 12 arylene, xylylene, a -CH 2 -CH (OH) -CH 2 group or a group -CH 2 -CH (OH) -CH 2 -OXO-CH 2 -CH (OH) -CH 2 - means , wherein XC 2 -C 10 alkylene, C 6 -C 15 arylene or C 6 -C 12 cycloalkylene, or, provided that R 15 is not alkanoyl, alkenoyl or benzoyl, R 16 is also a divalent radical of an aliphatic, cycloaliphatic or can mean aromatic dicarboxylic acid or dicarbamic acid, or R 15 and R 16 together if c = 1, the cyclisc hen residue may be an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Stellen etwaige Substituenten C1-C12 Alkyl, C5-C8 Cycloalkyl oder C2-C12 Alkylen dar, so haben sie die bereits unter a) angegebene Bedeutung.If any substituents are C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl or C 2 -C 12 alkylene, they have the meaning already given under a).

Als C7-C8 Aralkyl ist R15 insbesondere Phenylethyl oder vor allem Benzyl.

  • R15 ist als C2-C18 Alkanoyl beispielsweise Propionyl, Butyryl, Octanoyl, Dodecanoyl, Hexadecanoyl, Octadecanoyl aber bevorzugt Acetyl und als C3-C5 Alkenoyl insbesondere Acryloyl.
As C 7 -C 8 aralkyl, R 15 is in particular phenylethyl or especially benzyl.
  • R 15 as C 2 -C 18 alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl but preferably acetyl and as C 3 -C 5 alkenoyl especially acryloyl.

Bedeutet R16 ein gegebenenfalls mit einer Cyano-, Carbonyl- oder Carbamidgruppe substituiertes C2-C8 Alkenyl, dann handelt es sich z.B. um 1-Propenyl, Allyl, Methallyl, 2-Butenyl, 2-Pentenyl, 2-Hexenyl, 2-Octenyl, 2,2-Dicyanovinyl, 1-Methyl-2-cyano-2-methoxycarbonyl-vinyl, 2,2-Diacetylaminovinyl.If R 16 is a C 2 -C 8 alkenyl optionally substituted with a cyano, carbonyl or carbamide group, then it is, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2- Octenyl, 2,2-dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonyl-vinyl, 2,2-diacetylaminovinyl.

Bedeuten etwaige Substituenten C6-C15 Arylen, so stellen sie z.B. o-, m- oder p-Phenylen, 1,4-Naphthylen oder 4,4'-Diphenylen dar.Any C 6 -C 15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Als C6-C12 Cycloalkylen ist X insbesondere Cyclohexylen.As C 6 -C 12 cycloalkylene, X is in particular cyclohexylene.

Beispiele für Polyalkylpiperidinverbindungen dieser Klasse sind in der nachfolgenden Tabelle II aufgeführt.

Figure imgb0013
Examples of polyalkylpiperidine compounds of this class are listed in Table II below.
Figure imgb0013

c) Verbindungen der Formel IV

Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
ist, worin R17 Wasserstoff, C1-C12 Alkyl, eine Gruppe -CH2-OCOR22 ist, worin R22 Wasserstoff, C1-C4 Alkyl, C2-C6 Alkenyl, Cyclohexyl, Phenyl, Benzyl oder Chlormethyl ist, eine Gruppe -CH20-S(O)qR23, worin R23 C1-C4 Alkyl, p-Tolyl oder Phenyl ist und q die Zahlen 1 oder 2 bedeutet, wo R17 eine Gruppe -CH2OCO-NHR24 bedeutet, worin R24 Wasserstoff oder C1-C4 Alkyl ist, R18 Wasserstoff oder C1-C4 Alkyl bedeutet, R19 Wasserstoff, C1-C12 Alkyl, C3-C4 Alkoxyalkyl, C5-C8 Cycloalkyl, Allyl oder Benzyl bedeutet, R20 Wasserstoff, C1-C12 Alkyl, C5-C8 Cycloalkyl oder Benzyl, R21 C1-C12 Alkyl, C5-C8 Cycloalkyl oder Phenyl sind oder R20 und R21 zusammen mit dem C-Atom an das sie gebunden sind einen C5-C12 Cycloalkan oder Alkylcycloalkanring bilden, und W zusätzlich auch eine der Gruppen der Formeln
Figure imgb0018
Figure imgb0019
oder
Figure imgb0020
ist, worin g die Zahlen 1 bis 12 bedeutet.c) compounds of the formula IV
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
 is where R 17 is hydrogen, C 1 -C 12 alkyl, a group -CH 2 -OCOR 22 , wherein R 22 is hydrogen, C 1 -C 4 alkyl, C 2 -C 6 alkenyl, cyclohexyl, phenyl, benzyl or chloromethyl is a group -CH 2 O-S (O) qR 23 , wherein R 23 is C 1 -C 4 alkyl, p-tolyl or phenyl and q represents the numbers 1 or 2, where R 17 represents a group -CH 2 OCO -NHR 24 means wherein R 24 is hydrogen or C 1 -C 4 alkyl, R 18 is hydrogen or C 1 -C 4 alkyl, R 19 is hydrogen, C 1 -C 12 alkyl, C 3 -C 4 alkoxyalkyl, C 5 -C 8 denotes cycloalkyl, allyl or benzyl, R 20 denotes hydrogen, C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl or benzyl, R 21 C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl or phenyl or R 20 and R 21 together with the carbon atom to which they are attached form a C 5 -C 12 cycloalkane or alkylcycloalkane ring, and W additionally also one of the groups of the formulas
Figure imgb0018
Figure imgb0019
 or
Figure imgb0020
 is where g is the numbers 1 to 12.

Stellen etwaige Substituenten C1-C4 oder C1-C12 Alkyl oder C5-C8 Cycloalkyl dar, so haben sie die bereits unter a) angegebene Bedeutung.

  • R19 bedeutet als C3-C4 Alkoxyalkyl z. B. Ethoxymethyl, 2-Methoxyethyl oder 2-Ethoxyethyl.
  • R22 ist als C2-C6 Alkenyl z. B. Vinyl, Allyl, Methallyl, Dimethylallyl oder 2-Hexenyl.
  • Beispiele für Polyalkylpiperidinverbindungen dieser Klasse sind in der nachstehenden Tabelle III aufgeführt.
    Figure imgb0021
If any substituents are C 1 -C 4 or C 1 -C 12 alkyl or C 5 -C 8 cycloalkyl, they have the meaning already given under a).
  • R 19 as C 3 -C 4 alkoxyalkyl z. B. ethoxymethyl, 2-methoxyethyl or 2-ethoxyethyl.
  • R 22 is as C 2 -C 6 alkenyl z. B. vinyl, allyl, methallyl, dimethylallyl or 2-hexenyl.
  • Examples of polyalkylpiperidine compounds of this class are listed in Table III below.
    Figure imgb0021

Ebenfalls typische Vertreter dieser Klasse von Verbindungen sind die Verbindungen 16 und 17:

Figure imgb0022
Figure imgb0023
d) Verbindungen der Formel V
Figure imgb0024
worin R und R1 die für Formel I angegebene Bedeutung haben, R25 eine Gruppe CrH2r ist, in welcher r eine Zahl 2 bis 12 bedeutet, oder C4-C8 Alkenylen, C4-C8 Alkinylen, Phenylen, Xylylen, Bitolylen, C5-C12 Cycloalkylen oder eine Gruppe -CH2CH(OY)CH2-(OCH2-CH(OY)CH2)2- ist, worin Y Wasserstoff, C1-C18 Alkyl, Allyl, Benzyl, C2-C12 Alkanoyl oder Benzoyl ist oder R25 eine Gruppe -CONH-B-NHCO- ist, worin B eine Gruppe CrH2r, Phenylen, Naphthylen, Tolylen oder eine Gruppe der Formeln
Figure imgb0025
oder
Figure imgb0026
bedeutet, worin R26 Wasserstoff oder Methyl und R27 Wasserstoff, Methyl oder Ethyl sind.

  • R25 bedeutet als C4-C8 Alkenylen z. B. 2-Butenylen-1,4.
  • R25 bedeutet als C4-C8 Alkinylen z.B. 2-Butinylen-1,4.
Typical representatives of this class of compounds are compounds 16 and 17:
Figure imgb0022
Figure imgb0023
 d) compounds of formula V
Figure imgb0024
 wherein R and R 1 have the meaning given for formula I, R 25 is a group C r H 2r , in which r is a number 2 to 12, or C 4 -C 8 alkenylene, C 4 -C 8 alkynylene, phenylene, Xylylene, bitolylene, C 5 -C 12 cycloalkylene or a group -CH 2 CH (OY) CH 2 - (OCH 2 -CH (OY) CH 2 ) 2 -, wherein Y is hydrogen, C 1 -C 18 alkyl, allyl , Benzyl, C 2 -C 12 alkanoyl or benzoyl or R 25 is a group -CONH-B-NHCO-, wherein B is a group C r H 2r , phenylene, naphthylene, tolylene or a group of the formulas
Figure imgb0025
 or
Figure imgb0026
 means where R 26 is hydrogen or methyl and R 27 is hydrogen, methyl or ethyl.
  • R 25 as C 4 -C 8 alkenylene z. B. 2-butenylene-1,4.
  • R 25 as C 4 -C 8 alkynylene, for example 2-butynylene-1,4.

Als C5-C12 Cycloalkylen bedeutet R25 z. B. Cyclopentylen, Cyclohexylen, Cyclooctylen, Cyclodecylen oder Cyclododecylen. Bevorzugt ist Cyclohexylen.As C 5 -C 12 cycloalkylene R 25 means z. B. cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene or cyclododecylene. Cyclohexylene is preferred.

Y bedeutet als C1-C18 Alkyl z. B. Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, 2,2-Dimethylpropyl, n-Hexyl, 2,3-Dimethylbutyl, n-Octyl, 1,1,3,3-Tetramethylbutyl, Nonyl, Decyl, Dodecyl, Hexadecyl oder Octadecyl.Y is C 1 -C 18 alkyl z. B. methyl, ethyl, propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, 2,3-dimethylbutyl, n-octyl, 1, 1,3,3-tetramethylbutyl, nonyl, decyl, dodecyl, hexadecyl or octadecyl.

Bedeutet Y C2-C12 Alkanoyl, so stellt es beispielsweise Propionyl, Butyryl, Octanoyl, Dodecanoyl, aber bevorzugt Acetyl dar.If YC 2 -C 12 alkanoyl, it is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

Beispiele für Polyalkylpiperidinverbindungen dieser Klasse sind die folgenden Verbindungen 18 und 19Examples of polyalkylpiperidine compounds of this class are the following compounds 18 and 19

Figure imgb0027
Figure imgb0028
e) Verbindungen der Formel VI
Figure imgb0029
worin d die Zahlen 1 oder 2 ist und R28 eine Gruppe der Formel
Figure imgb0030
bedeutet, worin R und R1 die für Formel I angegebene Bedeutung haben, Q-O- oder -N(R31)- ist, A C2-C6 Alkylen und m die Zahlen 0 oder 1 bedeuten, R29 die Gruppen R28, NR31R32, -OR33, -NHCH20R33 oder -N(CH2OR33)2 ist, R30, wenn d = 1 die Gruppen R28 oder R29 und wenn d = 2 die Gruppe -Q-D-Q-, worin D ununterbrochenes oder durch -N(R34)- unterbrochenes C2-C6 Alkylen bedeutet, R31 Wasserstoff, C1-C12 Alkyl, Allyl, Cyclohexyl, Benzyl oder C1-C4 Hydroxyalkyl oder eine Gruppe der Formel
Figure imgb0031
ist, R32 C1-C12 Alkyl, Allyl, Cyclohexyl, Benzyl, C1-C4 Hydroxyalkyl, R33 C1-C12 Alkyl oder Phenyl und R34 Wasserstoff oder die Gruppe -CH20R33 bedeuten oder R31 und R32 zusammen C4-C5 Alkylen oder Oxaalkylen sind oder auch R31 und R32 jeweils eine Gruppe der Formel
Figure imgb0032
Figure imgb0027
Figure imgb0028
 e) compounds of the formula VI
Figure imgb0029
 wherein d is the number 1 or 2 and R 28 is a group of the formula
Figure imgb0030
 means in which R and R 1 have the meaning given for formula I, QO- or -N (R 31 ) -, AC 2 -C 6 alkylene and m are the numbers 0 or 1, R 29 is the groups R 28 , NR 31 is R 32 , -OR 33 , -NHCH 2 0R 33 or -N (CH 2 OR 33 ) 2 , R 30 if d = 1 the groups R 28 or R 29 and if d = 2 the group -QDQ-, wherein D is continuous or interrupted by -N (R 34 ) - C 2 -C 6 alkylene, R 31 is hydrogen, C 1 -C 12 alkyl, allyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl or a group of the formula
Figure imgb0031
 R 32 is C 1 -C 12 alkyl, allyl, cyclohexyl, benzyl, C 1 -C 4 hydroxyalkyl, R 33 C 1 -C 12 alkyl or phenyl and R 34 is hydrogen or the group -CH 2 0R 33 or R 31 and R 32 together are C 4 -C 5 alkylene or oxaalkylene or R 31 and R 32 are each a group of the formula
Figure imgb0032

Stellen etwaige Substituenten C1-C12 Alkyl dar, so haben sie die bereits unter a) angegebene Bedeutung.If any substituents are C 1 -C 12 alkyl, they have the meaning already given under a).

Bedeuten R31 und R32 C1-C4 Hydroxyalkyl, so stellen sie z.B. 2-Hydroxyethyl, 2-Hydroxypropyl, 3-Hydroxypropyl, 2-Hydroxybutyl oder 4-Hydroxybutyl dar.If R 31 and R 32 are C 1 -C 4 hydroxyalkyl, they are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Bedeuten A oder D C2-C6 Alkylen, so stellen sie beispielsweise Ethylen, Propylen, 2,2-Dimethyipropylen, Tetramethylen oder Hexamethylen dar.If A or DC is 2 -C 6 alkylene, they are, for example, ethylene, propylene, 2,2-dimethyl propylene, tetramethylene or hexamethylene.

Stellen R31 und R32 zusammen C4-C5 Alkylen oder Oxaalkylen dar, so bedeutet dies z. B. Tetramethylen, Pentamethylen oder 3-Oxa-pentamethylen.If R 31 and R 32 together represent C4-C5 alkylene or oxaalkylene, this means, for. B. tetramethylene, pentamethylene or 3-oxapentamethylene.

Beispiele für Polyalkylpiperidinverbindungen dieser Klasse sind in der nachstehenden Tabelle IV aufgeführt:

Figure imgb0033
Examples of polyalkylpiperidine compounds of this class are listed in Table IV below:
Figure imgb0033

Ein weiteres Beispiel für Verbindungen dieser Klasse ist folgende Verbindung 23

Figure imgb0034
Figure imgb0035
f) Verbindungen der Formel VII
Figure imgb0036
worin e die Zahlen 1 oder 2 bedeutet, R Wasserstoff oder Methyl ist und R35, wenn e = 1, C4-C18 Alkyl, C7-C12 Aralkyl, die Gruppe -CO-R36, C1-C4 Alkyl substituiert durch -CN, -COOR37, -OH, -OCOR38 oder
Figure imgb0037
wobei R36 C1-C12 Alkyl, Cz-C4 Alkenyl oder Phenyl, R37 C1-C18 Alkyl, R38 C1-C18 Alkyl, C2-C10 Alkenyl, Cyclohexyl, Benzyl oder C6-C10 Aryl sind, oder, wenn e = 2, R35 C4-C12 Alkylen, 2-Butenylen-1,4, Xylylen, die Gruppen -(CH2)2-OOC-R39-COO-(CH2)2-, -CH2-OOC-R40-COO-CH2- oder -CH2-CH(OH)-CH2-O-R39-O-CH2-CH(OH)-CH2- ist, wobei R39 C2-C10 Alkylen, Phenylen, Cyclohexylen oder 2,2-Diphenylen-propan und R40 C2-C10 Alkylen, Xylylen oder Cyclohexylen bedeuten.Another example of compounds of this class is the following compound 23
Figure imgb0034
Figure imgb0035
 f) compounds of the formula VII
Figure imgb0036
 wherein e represents the numbers 1 or 2, R is hydrogen or methyl and R 35 , if e = 1, C 4 -C 18 alkyl, C 7 -C 12 aralkyl, the group -CO-R 36 , C 1 -C 4 Alkyl substituted by -CN, -COOR 37 , -OH, -OCOR 38 or
Figure imgb0037
 where R 36 is C 1 -C 12 alkyl, C z -C 4 alkenyl or phenyl, R 37 C 1 -C 18 alkyl, R 38 C 1 -C 18 alkyl, C 2 -C 10 alkenyl, cyclohexyl, benzyl or C 6 -C 10 are aryl, or if e = 2, R 35 C 4 -C 12 alkylene, 2-butenylene-1,4, xylylene, the groups - (CH 2 ) 2 -OOC-R 39 -COO- (CH 2 ) 2 -, -CH 2 -OOC-R 40 -COO-CH 2 - or -CH 2 -CH (OH) -CH 2 -OR 39 -O-CH 2 -CH (OH) -CH 2 -, where R 39 is C 2 -C 10 alkylene, phenylene, cyclohexylene or 2,2-diphenylene propane and R 40 is C 2 -C 10 alkylene, xylylene or cyclohexylene.

Bedeuten etwaige Substituenten C1-C12 Alkyl, so stellen sie z.B. Methyl, Ethyl, n-Propyl, n-Butyl, sek.-Butyl, tert.-Butyl, n-Hexyl, n-Octyl, 2-Ethyl-hexyl, n-Nonyl, n-Decyl, n-Undecyl oder n-Dodecyl dar.If any substituents are C 1 -C 12 alkyl, they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Etwaige Substituenten, die C1-C18 Alkyl bedeuten, können z.B. die oben angeführten Gruppen und dazu noch beispielsweise n-Tridecyl, n-Tetradecyl, n-Hexadecyl oder n-Octadecyl darstellen.Any substituents which are C 1 -C 18 alkyl can represent, for example, the groups mentioned above and, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Stellen etwaige Gruppen C2-C10 Alkylen dar, so bedeuten sie beispielsweise Ethylen, Propylen, 2,2-Dimethyl-propylen, Tetramethylen, Hexamethylen, Octamethylen oder Decamethylen.If any groups C2-C10 represent alkylene, they mean, for example, ethylene, propylene, 2,2-dimethyl-propylene, tetramethylene, hexamethylene, octamethylene or decamethylene.

R35 bedeutet als C4-C18 Alkyl z. B. n-Butyl, sek.-Butyl, tert.-Butyl, n-Hexyl, n-Octyl, 2-Ethyl-hexyl, n-Nonyl, n-Decyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Hexadecyl oder n-Octadecyl.R 35 as C 4 -C 18 alkyl z. B. n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n - decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Bedeutet R35 ein durch-CN substituiertes Cl-C4 Alkyl, so stellt es beispielsweise Cyanomethyl, Cyanoethyl, 3-Cyano-n-propyl, 4-Cyano-n-butyl dar.If R 35 is a C 1 -C 4 alkyl substituted by-CN, it is, for example, cyanomethyl, cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl.

Bedeutet R35 C4-C12 Alkylen, so handelt es sich z.B. um 2,2-Dimethylpropylen, Tetramethylen, Hexamethylen, Octamethylen, Decamethylen oder Dodecamethylen.If R 35 is C4-C12 alkylene, it is, for example, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Stellt R35 C7-C12 Aralkyl dar, so bedeutet es insbesondere Phenylethyl, p-Methyl-benzyl oder vor allem Benzyl.If R 35 is C 7 -C 12 aralkyl, it means in particular phenylethyl, p-methyl-benzyl or especially benzyl.

R36 bedeutet als C2-C4 Alkenyl beispielsweise Vinyl, 1-Propenyl, Allyl, Methallyl, 2-Butenyl.R 36 as C 2 -C 4 alkenyl means, for example, vinyl, 1-propenyl, allyl, methallyl, 2-butenyl.

R38 bedeutet als C2-C10 Alkenyl z.B. die für R36 in der Bedeutung Alkenyl angeführten Gruppen und dazu noch beispielsweise Crotyl, 2-Hexenyl, 2-Octenyl oder 2-Decenyl.As C 2 -C 10 alkenyl, R 38 means, for example, the groups mentioned for R 36 as alkenyl and, for example, crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.

Stellt R38 C6-C10 Aryl dar, so bedeutet es beispielsweise unsubstituiertes oder in o- oder p-Stellung durch Methyl, Ethyl, Isopropyl, n-Butyl oder tert.-Butyl substituiertes Phenyl.If R 38 is C 6 -C 10 aryl, it means, for example, phenyl which is unsubstituted or substituted in the o- or p-position by methyl, ethyl, isopropyl, n-butyl or tert-butyl.

Beispiele für Polyalkylpiperidinverbindungen dieser Klasse sind folgende Verbindungen:

  • 24) Bis-[2-(2,2,6,6-tetramethylpiperidino)-ethyl]-sebacat
  • 25) 1-Octoxycarbonyl-methyl-2,2,6,6-tetramethylpiperidin
  • 26) 1,4-Bis-(2,2,6,6-tetramethylpiperidino)-2-buten.
Examples of polyalkylpiperidine compounds of this class are the following compounds:
  • 24) Bis- [2- (2,2,6,6-tetramethylpiperidino) ethyl] sebacate
  • 25) 1-Octoxycarbonyl-methyl-2,2,6,6-tetramethylpiperidine
  • 26) 1,4-bis (2,2,6,6-tetramethylpiperidino) -2-butene.

g) Polymere Verbindungen ausgewählt aus der Gruppe bestehend aus Polyester, Polyether, Polyamide, Polyamine, Polyurethane, Polyharnstoffe, Polyaminotriazine, Poly(meth)acrylate, Poly-(meth)acrylamide und deren Copolymeren, deren wiederkehrende Struktureinheiten eine Gruppe der Formel 1 enthalten oder über eine bivalente Gruppe entsprechend der Formel (I), worin R1 eine freie Valenz bedeutet, verbunden sind, wobei im übrigen R und R1 die für Formel I angegebene Bedeutung haben.g) polymeric compounds selected from the group consisting of polyester, polyether, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and their copolymers, the recurring structural units of which contain a group of formula 1 or are connected via a bivalent group corresponding to formula (I), in which R 1 is a free valence, where R and R 1 have the meaning given for formula I.

Beispiele für Polyalkylpiperidinverbindungen dieser Klasse sind die Verbindungen der folgenden Formeln, wobei m die Zahlen 2 bis etwa 200 bedeutet.

Figure imgb0038
Figure imgb0039
Figure imgb0040
 Examples of polyalkylpiperidine compounds of this class are the compounds of the following formulas, where m denotes the numbers 2 to about 200.
Figure imgb0038
Figure imgb0039
Figure imgb0040

h) Verbindungen der Formel VIII

Figure imgb0041
worin R41 ein Rest der Formel IX bedeutet
Figure imgb0042
und worin j 1 oder 2 ist und die Reste R1 und R die für Formel I definierte Bedeutung besitzen. Beispiele für Polyalkylpiperidinverbindungen der Formel VIII sind in der nachfolgenden Tabelle V aufgeführt.
Figure imgb0043
 h) compounds of the formula VIII
Figure imgb0041
 wherein R 41 is a radical of formula IX
Figure imgb0042
 and wherein j is 1 or 2 and the radicals R 1 and R have the meaning defined for formula I. Examples of polyalkylpiperidine compounds of the formula VIII are listed in Table V below.
Figure imgb0043

Die als Komponente i) erfindungsgemäss einzusetzenden Polyalkylpiperidinverbindungen sind allgemein bekannt.The polyalkylpiperidine compounds to be used as component i) according to the invention are generally known.

Die als Komponente ii) geeigneten phenolischen Antioxidantien sind allgemein bekannt. Es können z.B. folgende genannt werden:

  • 1. Alkylierte Monophenole
    • 2,6-Di-tert.-butyl-4-methylphenol
    • 2-Tert.-butyl-4,6-dimethylphenol
    • 2,6-Di-tert.-butyl-4-ethylphenol
    • 2,6-Di-tert.-butyl-4-n-butylphenol
    • 2,6-Di-tert.-butyl-4-n-butylphenol
    • 2,6-Di-cyclopentyl-4-methylphenol
    • 2-(α-Methylcyclohexyl)-4,6-dimethylphenol
    • 2,6-Di-octadecyl-4-methylphenol
    • 2,4,6-Tri-cyclohexylphenol
    • 2,6-Di-tert.-butyl-4-methoxymethylphenol
  • 2. Alkylierte Hydrochinone
    • 2,6-Di-tert.-butyl-4-methoxyphenol
    • 2.5-Di-tert.-butyl-hydrochinon
    • 2,5-Di-tert.-amyl-hydrochinon
    • 2,6-Diphenyl-4-octadecyloxyphenol
  • 3. Alkyliden-Bisphenole
    • 2,2'-Methylen-bis-(6-tert.-butyl-4-methylphenol)
    • 2,2'-Methylen-bis-(6-tert.-butyl-4-ethylphenol)
    • 2,2'-Methylen-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]
    • 2,2'-Methylen-bis-(4-methyl-6-cyclohexylphenol)
    • 2,2'-Methylen-bis-(6-nonyl-4-methylphenol)
    • 2,2'-Methylen-bis-(4,6-di-tert.-butylphenol)
    • 2,2'-Ethyliden-bis-(4,6-di-tert.-butylphenol)
    • 2,2'-Ethyliden-bis-(6-tert.-butyl-4-isobutylphenol)
    • 4,4'-Methylen-bis-(2,6-di-tert.-butylphenol)
    • 4,4'-Methylen-bis-(6-tert.-butyl-2-methylphenol)
    • 1,1-Bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butan
    • 2,6-Di-(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
    • 1,1,3-Tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butan
    • 1,1-Bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutan
    • Ethylenglycol-bis-[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)-butyrat]
    • Di-(3-tert.-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadien
    • Di-[2-(3'-tert.-butyλ-2'-hydroxy-5'-methyλ-benzyλ)-6-tert.-butyl-4-methyλ-phenyl]-terephthalat.
  • 4. Benzylverbindungen
    • 1,3,5-Tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol
    • Di-(3,5-di-tert.-butyl-4-hydroxybenzyl)-sulfid
    • 3,5-Di-tert.-butyl-4-hydroxybenzyl-mercaptoessigsäure-isooctylester
    • Bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol-terephthalat
    • 1,3,5-Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-isocyanurat
    • 1,3,5-Tris-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurat
    • 3,5-Di-tert.-butyl-4-hydroxybenzyl-phosphonsäure-dioctadecylester
    • 3,5-Di-tert.-butyl-4-hydroxybenzyl-phosphonsäure-monoethylester
    • Calciumsalz.
  • 5. Acylaminophenole
    • 4-Hydroxy-laurinsäureanilid
    • 4-Hydroxy-stearinsäureanilid
    • 2,4-Bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxyanilino)-s-triazin
  • 6. Ester der ß-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-
    • propionsäure mit ein- oder mehrwertigen Alkoholen, wie z.B. mit
      Figure imgb0044
      Figure imgb0045
  • 7. Ester der 3,5-Di-tert.-butyl-4-hydroxyphenyl-
    • benzoesäure
    • Pentaerythritol-tetrakis-(3,5-di-tert.-butyl-4-hydroxybenzoat)
    • 2,4-Di-tert.-butylphenyl-(3,5-di-tert.-butyl-4-hydroxybenzoat)
  • 8. Ester der ß-(5-tert.-Butyl-4-hydroxy-3-methyl-
    • phenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen, wie z.B. mit
      Figure imgb0046
  • 9. Amide der ß-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-propionsäure
    • wie z. B.
    • N,N'-Di-(3,5-di-tert.-butyl-4-hydroxyphenyl- propionyl)-hexamethylendiamin
    • N,N'-Di-(3,5-di-tert.-butyl-4-hydroxyphenyl- propionyl)-trimethylendiamin
    • N,N'-Di-(3,5-di-tert.-butyl-4-hydroxyphenyl- propionyl)-hydrazin.
  • 10. Triazinphenole, wie beispielsweise die Verbindung der Formel X
    Figure imgb0047
The phenolic antioxidants suitable as component ii) are generally known. For example, the following can be mentioned:
  • 1. Alkylated monophenols
    • 2,6-di-tert-butyl-4-methylphenol
    • 2-tert-butyl-4,6-dimethylphenol
    • 2,6-di-tert-butyl-4-ethylphenol
    • 2,6-di-tert-butyl-4-n-butylphenol
    • 2,6-di-tert-butyl-4-n-butylphenol
    • 2,6-di-cyclopentyl-4-methylphenol
    • 2- (α-methylcyclohexyl) -4,6-dimethylphenol
    • 2,6-di-octadecyl-4-methylphenol
    • 2,4,6-tri-cyclohexylphenol
    • 2,6-di-tert-butyl-4-methoxymethylphenol
  • 2. Alkylated hydroquinones
    • 2,6-di-tert-butyl-4-methoxyphenol
    • 2,5-di-tert-butyl hydroquinone
    • 2,5-di-tert-amyl hydroquinone
    • 2,6-diphenyl-4-octadecyloxyphenol
  • 3. Alkylidene bisphenols
    • 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol)
    • 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol)
    • 2,2'-methylene-bis- [4-methyl-6- (α-methylcyclohexyl) phenol]
    • 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol)
    • 2,2'-methylene-bis- (6-nonyl-4-methylphenol)
    • 2,2'-methylene-bis- (4,6-di-tert-butylphenol)
    • 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol)
    • 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol)
    • 4,4'-methylene-bis- (2,6-di-tert-butylphenol)
    • 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol)
    • 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane
    • 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol
    • 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane
    • 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane
    • Ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate]
    • Di- (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene
    • Di- [2- (3'-tert-butyλ-2'-hydroxy-5'-methyλ-benzyλ) -6-tert-butyl-4-methyλ-phenyl] terephthalate.
  • 4. Benzyl compounds
    • 1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene
    • Di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide
    • 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester
    • Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate
    • 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate
    • 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate
    • 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester
    • 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester
    • Calcium salt.
  • 5. Acylaminophenols
    • 4-hydroxy lauric anilide
    • 4-hydroxy stearic anilide
    • 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine
  • 6. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -
    • propionic acid with mono- or polyhydric alcohols, such as with
      Figure imgb0044
      Figure imgb0045
  • 7. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl
    • benzoic acid
    • Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxybenzoate)
    • 2,4-di-tert-butylphenyl- (3,5-di-tert-butyl-4-hydroxybenzoate)
  • 8. Esters of β- (5-tert-butyl-4-hydroxy-3-methyl-
    • phenyl) propionic acid with mono- or polyhydric alcohols, such as with
      Figure imgb0046
  • 9. Amides of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid
    • such as B.
    • N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hexamethylene diamine
    • N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) trimethylene diamine
    • N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hydrazine.
  • 10. triazine phenols, such as the compound of formula X.
    Figure imgb0047

Folgende phenolische Antioxidantien sind als Komponente ii) bevorzugt:

  • 1) 2,6-Di-tert.-butyl-4-methylphenol,
  • 2) 2,2'-Methylen-bis-(6-tert.-butyl-4-methylphenol),
  • 3) 2,2'-Methylen-bis-(6-tert.-butyl-4-ethylphenol),
  • 4) 4,4'-Methylen-bis-(2,6-di-tert.-butylphenol),
  • 5) 2,2-Bis-(2,6-di-tert.-butyl-4-hydroxyphenyl)-propan,
  • 6) 2,2'-Methylen-bis-[4-methyl-6-(a-methylcyclohexyl)-phenol],
  • 7) 1,1-Bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butan,
  • 8) 1,1,3-Tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butan,
  • 9) Ethylenglycol-bis-[3,3-bis-(3-tert.-butyl-4-hydroxyphenyl)-butyrat],
  • 10) 4,4'-Thio-bis-(6-tert.-butyl-3-methylphenol),
  • 11) 1,3,5-Tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol,
  • 12) Triethylenglycol-bis-(3-methyl-5-tert.-butyl-4-hydroxyphenyl)-propionat,
  • 13) 1,3,5-Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-isocyanurat,
  • 14) 3,5-Di-tert.-butyl-4-hydroxybenzyl-phosphonsäure-diethylester,
  • 15) N,N'-Di-(3,5-di-tert.-butyl-4-hydroxyphenyl- propionyl)-hexamethylendiamin,
  • 16) 3-Thia-1,5-pentandiol-bis-[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionat],
  • 17) 1,6-Hexandiol-bis-[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionat],
  • 18) Pentaerythritol-tetrakis-[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionat],
  • 19) Pentaerythritol-tetrakis-(3,5-di-tert.-butyl-4-hydroxybenzoat),
  • 20) Octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionat,
  • 21) 2-(3,5-Di-tert.-butyl-4-hydroxyanilino)-4,6-di-(octylthio)-triazin,
  • 22) 2,4-Di-tert.-butylphenyl-(3,5-di-tert.-butyl-4-hydroxybenzoat),
  • 23) das Phenol der Formel XI
    Figure imgb0048
  • 24) das Phenol der Formel X
    Figure imgb0049
The following phenolic antioxidants are preferred as component ii):
  • 1) 2,6-di-tert-butyl-4-methylphenol,
  • 2) 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol),
  • 3) 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol),
  • 4) 4,4'-methylene-bis- (2,6-di-tert-butylphenol),
  • 5) 2,2-bis (2,6-di-tert-butyl-4-hydroxyphenyl) propane,
  • 6) 2,2'-methylene-bis- [4-methyl-6- (a-methylcyclohexyl) phenol],
  • 7) 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
  • 8) 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
  • 9) ethylene glycol bis- [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate],
  • 10) 4,4'-thio-bis- (6-tert-butyl-3-methylphenol),
  • 11) 1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
  • 12) triethylene glycol bis (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate,
  • 13) 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
  • 14) diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
  • 15) N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine,
  • 16) 3-thia-1,5-pentanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
  • 17) 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
  • 18) pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
  • 19) pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxybenzoate),
  • 20) octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
  • 21) 2- (3,5-di-tert-butyl-4-hydroxyanilino) -4,6-di- (octylthio) triazine,
  • 22) 2,4-di-tert-butylphenyl- (3,5-di-tert-butyl-4-hydroxybenzoate),
  • 23) the phenol of formula XI
    Figure imgb0048
  • 24) the phenol of formula X
    Figure imgb0049

Das erfindungsgemässe Stabilisatorgemisch kann allein oder zusammen mit anderen Verbindungen in bekannter Weise in ein photographisches Material eingearbeitet werden.The stabilizer mixture according to the invention can be incorporated into a photographic material alone or together with other compounds in a known manner.

Das Mischungsverhältnis von dem Polyalkylpiperidin-Lichtschutzmittel i) zum phenolischen Antioxidans ii) variiert beispielsweise zwischen 90 : 10 und 10 : 90, bevorzugt zwischen 70 : 30 und 30 : 70.The mixing ratio of the polyalkylpiperidine light stabilizer i) to the phenolic antioxidant ii) varies, for example, between 90:10 and 10:90, preferably between 70:30 and 30:70.

In der Regel wird das Stabilisatorgemisch allein oder zusammen mit anderen Verbindungen, insbesondere mit den Farbkupplern, in Form einer Dispersion in das photographische Material eingearbeitet, wobei diese Dispersion entweder kein Lösungsmittel oder hoch- oder tiefsiedende Lösungsmittel oder ein Gemisch solcher Lösungsmittel enthält. Eine weitere geeignete Einarbeitungsform besteht darin, dass man die Stabilisatoren allein oder zusammen mit weiteren Verbindungen zusammen mit einem Polymer in Form eines Latex in das photographische Material einarbeitet.As a rule, the stabilizer mixture, alone or together with other compounds, in particular with the color couplers, is incorporated into the photographic material in the form of a dispersion, this dispersion either containing no solvent or high or low-boiling solvent or a mixture of such solvents. Another suitable form of incorporation is that the stabilizers are incorporated into the photographic material alone or together with other compounds together with a polymer in the form of a latex.

Die Dispersionen werden dann zur Herstellung der Schichten von farbphotographischen Aufzeichnungsmaterialien verwendet. Diese Schichten können z. B. Zwischen- oder Schutzschichten, insbesondere jedoch lichtempfindliche (blau-, grün- und rot-empfindliche) 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 are then used to produce the layers of color photographic recording materials. These layers can e.g. B. Intermediate or protective layers, but especially photosensitive (blue, green and red sensitive) silver halide emulsion layers, in which in the development of the exposed recording material from the corresponding color couplers, the cyan (cyan) -, magenta (magenta) - and Yellow dyes are formed.

Die Silberhalogenidschichten können beliebige Farbkuppler, insbesondere Blaugrün-, Purpur-und Gelb-Kuppler, die zur Bildung der genannten Farbstoffe und damit der Farbbildner verwendet werden, enthalten.The silver halide layers can contain any desired color couplers, in particular cyan, magenta and yellow couplers, which are used to form the dyes mentioned and thus the color formers.

Da das Substrat die Wirkung und Stabilität der Stabilisatorgemische beeinflusst, werden Substrate (Lösungsmittel, Polymere) bevorzugt, die zusammen mit den Stabilisatoren eine möglichst gute Beständigkeit der zu stabilisierenden Materialien ergeben.Since the substrate influences the effect and stability of the stabilizer mixtures, substrates (solvents, polymers) are preferred which, together with the stabilizers, give the materials to be stabilized as good a resistance as possible.

In der Regel werden die Stabilisatorgemische in Schichten eingearbeitet, die zusätzlich eine nach üblichen Methoden hergestellte und sensibilisierte Silberhalogenid-Dispersion enthalten. Sie können jedoch auch in zu Silberhalogenid enthaltenden Schichten benachbarten Schichten vorhanden sein.As a rule, the stabilizer mixtures are incorporated in layers which additionally contain a silver halide dispersion which has been prepared and sensitized by customary methods. However, they can also be present in layers adjacent to layers containing silver halide.

Die erfindungsgemässen photographischen Materialien besitzen einen üblichen Aufbau und Komponenten, die die Wirksamkeit der Stabilisatorgemische verstärken oder zumindest nicht nachteilig beeinflussen.The photographic materials according to the invention have a customary structure and components which enhance the effectiveness of the stabilizer mixtures or at least do not adversely affect them.

Im farbphotographischen Aufzeichnungsmaterial gemäss vorliegender Erfindung können die Stabilisatorgemische enthaltend die Komponenten i) und ii) ausser mit den FarbkuppJern zusätzlich auch mit Ultraviolettabsorbern oder anderen Lichtschutzmitteln in der gleichen Schicht kombiniert werden.In the color photographic recording material according to the present invention, the stabilizer mixtures containing components i) and ii) can also be combined with ultraviolet absorbers or other light stabilizers in the same layer in addition to the color couplers.

Wenn die Diffusionstransfermethode angewendet wird, kann das Stabilisatorgemisch auch in eine Empfangsschicht eingearbeitet werden.If the diffusion transfer method is used, the stabilizer mixture can also be incorporated into a receiving layer.

Die erfindungsgemässen farbphotographischen Materialien können in bekannter Weise verarbeitet werden. Ferner können sie im Verlauf oder nach der Verarbeitung in einer Weise behandelt werden, die ihre Stabilität weiter erhöht, beispielsweise durch die Behandlung in einem Stabilisatorbad oder das Aufbringen eines Schutzüberzuges.The color photographic materials according to the invention can be processed in a known manner be tested. Furthermore, they can be treated in the course or after processing in a manner which further increases their stability, for example by treatment in a stabilizer bath or the application of a protective coating.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung von photographischen Farbbildern durch bildmässige Belichtung und Farbentwicklung eines farbphotographischen Aufzeichnungsmaterials enthaltend ein Stabilisatorgemisch mit den Komponenten i) und ii). Weiterhin betrifft die Erfindung die nach diesem Verfahren erhaltenen photographischen Farbbilder.The invention further relates to a process for the production of color photographic images by imagewise exposure and color development of a color photographic recording material containing a stabilizer mixture with components i) and ii). The invention further relates to the photographic color images obtained by this process.

Die erfindungsgemäss einzusetzenden Stabilisatorgemische eignen sich in gewissen Fällen auch zum Schutz farbphotographischer Schichten, in denen die Farbstoffe direkt in die Emulsion eingelagert werden und das Bild durch selektive Bleichung erzeugt wird.In certain cases, the stabilizer mixtures to be used according to the invention are also suitable for protecting color photographic layers in which the dyes are incorporated directly into the emulsion and the image is produced by selective bleaching.

Die Menge des Stabilisatorgemisches kann in weiten Grenzen schwanken und liegt etwa im Bereich von 1 bis 2000 mg, vorzugsweise 100 bis 800 und insbesondere 200 bis 500 mg pro m2 der Schicht, in die es eingearbeitet wird.The amount of stabilizer mixture can vary within wide limits and is approximately in the range from 1 to 2000 mg, preferably 100 to 800 and in particular 200 to 500 mg per m 2 of the layer into which it is incorporated.

Falls das photographische Material einen oder mehrere UV-Absorber enthält, so kann dieser mit dem Stabilisatorgemisch zusammen in einer Schicht oder auch in einer benachbarten Schicht vorhanden sein. Die Menge an UV-Absorber kann in weiten Grenzen schwanken und liegt etwa im Bereich von 200-2000 mg, vorzugsweise 400-1000 mg pro m2 der Schicht. Beispiele für geeignete UV-Absorber sind solche vom Benzophenon-, Acrylnitril-, Thiazolidon-, Benztriazol-, Oxazol-, Thiazol- und Imidazoltyp.If the photographic material contains one or more UV absorbers, this can be present together with the stabilizer mixture in one layer or in an adjacent layer. The amount of UV absorber can vary within wide limits and is approximately in the range of 200-2000 mg, preferably 400-1000 mg per m 2 of the layer. Examples of suitable UV absorbers are those of the benzophenone, acrylonitrile, thiazolidone, benzotriazole, oxazole, thiazole and imidazole type.

Die mit dem erfindungsgemässen Aufzeichnungsmaterial durch Belichtung und Entwicklung erhaltenen Farbbilder zeigen eine sehr gute Lichtechtheit gegenüber sichtbarem und ultraviolettem Licht. Die Stabilisatorgemische i) + ii) 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 wässrigen 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 Stabilisatorgemische i) + ii) 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 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 Photographic Process 4. Auflage, Macmillan, New York, N.Y. 1977, Seite 23 ff., S. 166 ff.).The color images obtained by exposure and development with the recording material according to the invention show very good light fastness to visible and ultraviolet light. The stabilizer mixtures i) + ii) 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 their precipitation or crystallization can be 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 stabilizer mixtures i) + ii). Furthermore, the so-called pressure fog formation that frequently occurs with blue-sensitive emulsions can be largely suppressed. This can e.g. B. occur when photographic materials (silver halide emulsion layers, which are located on a support made of natural or synthetic materials) mechanical stresses, for. B. turning, bending or rubbing can be exercised during manufacture or during treatment prior to development. (T. H. James, The Theory of Photographic Process 4th Edition, Macmillan, New York, N.Y. 1977, pages 23 ff., P. 166 ff.).

AnwendungsbeispieleExamples of use 1. Testsubstanzen1. Test substances 1.1 Phenole1.1 phenols

Figure imgb0050
Figure imgb0050
Figure imgb0051
Figure imgb0051
Figure imgb0052
Figure imgb0052
Figure imgb0053
Figure imgb0053

1.2 Piperidine1.2 Piperidines

Figure imgb0054
Figure imgb0054
Figure imgb0055
Figure imgb0055
Figure imgb0056
Figure imgb0056
Figure imgb0057
Figure imgb0057
Figure imgb0058
Figure imgb0058

2. Anwendungsbeispiel 12. Application example 1 0,093 g des Gelbkupplers der Formel0.093 g of the yellow coupler of the formula

Figure imgb0059
und die in der Tabelle 1 angegebenen Mengen eines sterisch gehinderten Phenols (Verbindungen a bis c) und eines Piperidins (Verbindungen A und B) werden in 2,0 ml eines Gemisches von Trikresylphosphat/Ethylacetat (1,5 g in 100 ml) gelöst. Zu dieser Lösung gibt man 7,0 ml einer 6%igen Gelatinelösung, 0,5 ml einer 8%igen Lösung des Netzmittels der Formel
Figure imgb0060
in Isopropanol/Wasser (3: 4) und 0,5 ml Wasser und emulgiert mit Ultraschall bei einer Leistung von 100 Watt während 5 Minuten.
Figure imgb0059
 and the amounts of a sterically hindered phenol (compounds a to c) and a piperidine (compounds A and B) given in Table 1 are dissolved in 2.0 ml of a mixture of tricresyl phosphate / ethyl acetate (1.5 g in 100 ml). To this solution are added 7.0 ml of a 6% gelatin solution, 0.5 ml of an 8% solution of the wetting agent of the formula
Figure imgb0060
 in isopropanol / water (3: 4) and 0.5 ml of water and emulsified with ultrasound at a power of 100 watts for 5 minutes.

Zu 2,5 ml der so erhaltenen Emulsion gibt man 2,0 ml einer Silberbromid-Emulsion mit einem Silbergehalt von 6,0 g pro Liter, 0,7 ml einer 1 %igen wässerigen Lösung des Härters der Formel

Figure imgb0061
und 3,8 ml Wasser, stellt das Gemisch auf einen pH-Wert von 6,5 und vergiesst es auf ein auf eine Glasplatte aufgezogenes substriertes, kunststoffbeschichtetes, weisses Papier.To 2.5 ml of the emulsion thus obtained are added 2.0 ml of a silver bromide emulsion with a silver content of 6.0 g per liter, 0.7 ml of a 1% aqueous solution of the hardener of the formula
Figure imgb0061
 and 3.8 ml of water, the mixture is brought to a pH of 6.5 and poured onto a subbed, plastic-coated, white paper mounted on a glass plate.

Nach dem Erstarren wird in einem Trockenschrank mit Umluft bei Raumtemperatur getrocknet.After solidification, drying is carried out in a drying cabinet with circulating air at room temperature.

Nach 7 Tagen werden auf 35 x 180 mm geschnittene Proben hinter einem Stufenkeil mit 3000 Lux - s belichtet und anschliessend im Extaprint 2"-Prozess der Firma Kodak verarbeitet.After 7 days, samples cut to 35 x 180 mm are exposed behind a step wedge with 3000 lux - s and then processed in the Extaprint 2 "process by Kodak.

Die so erhaltenen Gelbkeile werden in einem Atlas Weather-Ometer mit einer 2500 W-Xenonlampe mit total 42 kJoule/cm2 bestrahlt (eine Vergleichsprobe enthält kein Lichtschutzmittel).The yellow wedges obtained in this way are irradiated in an Atlas Weather-Ometer with a 2500 W xenon lamp with a total of 42 kJoules / cm 2 (a comparative sample contains no light stabilizer).

In Tabelle 1 sind die prozentualen Abnahmen der Gelbdichte bei einer ursprünglichen Remissionsdichte von 1,0 im Blau enthalten.

Figure imgb0062
Table 1 shows the percentage decreases in yellow density with an original reflectance density of 1.0 in blue.
Figure imgb0062

Aus Tabelle 1 ist ersichtlich, dass die Kombination eines sterisch gehinderten Phenols mit einemIt can be seen from Table 1 that the combination of a sterically hindered phenol with a

3. Anwendungsbeispiel 23. Application example 2

Es werden Proben wie in Beispiel 1 beschrieben hergestellt und bestrahlt, wobei jedoch das sterisch gehinderte Phenol und das Piperidin in mo-Piperidin eine gegenüber den einzelnen Komponenten verbesserte Lichtschutzwirkung ergibt. laren Anteilen bezogen auf den Gelbkuppler zugesetzt werden.Samples are prepared and irradiated as described in Example 1, but the sterically hindered phenol and the piperidine in mo-piperidine give an improved sun protection effect compared to the individual components. laren proportions are added based on the yellow coupler.

Tabelle 2 enthält die entsprechenden Dichteabnahmen.

Figure imgb0063
Table 2 contains the corresponding density decreases.
Figure imgb0063

Aus Tabelle 2 ist ersichtlich, dass man zu ähnlichen Resultaten wie in Anwendungsbeispiel 1It can be seen from Table 2 that results similar to those in Application Example 1 are obtained

4. Anwendungsbeispiel 34. Application example 3

Es werden Proben wie in den Beispielen 1 und 2 beschrieben hergestellt, die jedoch anstelle des kommt, wenn man anstelle von Gewichtsverhältnissen von Molverhältnissen ausgeht. dort verwendeten Gelbkupplers den Gelbkuppler der Formel

Figure imgb0064
enthalten. Diese werden in einem Atlas Weather Ometer" hinter einem Kodak Wratten" 2C-Filter mit total 105 kJoule/cm2 bestrahlt.Samples are produced as described in Examples 1 and 2, but instead of if molar ratios are used instead of weight ratios. there the yellow coupler used the yellow coupler of the formula
Figure imgb0064
 contain. These are irradiated in a Atlas Weather Ometer "behind a Kodak Wratten" 2C filter with a total of 105 kJoules / cm 2 .

Tabelle 3 enthält die hierbei erhaltenen prozentualen Dichteabnahmen am Maximum bei einer Ausgangs-Remissionsdichte von 1,0.

Figure imgb0065
Table 3 contains the percentage density decreases obtained at the maximum with an initial reflectance density of 1.0.
Figure imgb0065

Claims (24)

1. A colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, one interlayer and/or one protective layer, contains a stabiliser mixture comprising i) a compound which contains at least one group of the formula I
Figure imgb0105
or a polymer, the recurring structural units of which contain a group of the formula I or are linked via a bivalent group corresponding to the formula I, in which R1 is a free valency and in which, moreover, R is hydrogen or methyl and R1 is methyl, a group -CH2-C(R2) = C(R3)(R4),
Figure imgb0106
Figure imgb0107
Figure imgb0108
Figure imgb0109
Figure imgb0110
a and b one of the numbers 0, 1 or 2, R2, R3 and R4 independently of one another are hydrogen or C1-C3 alkyl, R5 is hydrogen or methyl, R6 is C1-C4 alkyl, R7 is C1-C12 alkyl, allyl, benzyl or cyclohexyl, R8 is C1-C12 alkyl, allyl, cyclohexyl, benzyl or phenyl, Rg is hydrogen, C1-C12 alkyl or allyl, or R8 and Rg, together with the N atom to which they are linked, form a 5-membered or 6-membered heterocyclic ring, and Rio is hydrogen, C4-C12 alkyl, C2-C6 alkenyl, chloromethyl, C5-C8 cycloalkyl, C7-C14 aralkyl or C7-C10 alkylphenyl, R11 is hydrogen, C1-C4 alkyl, C2-C13 alkoxymethyl, phenyl or phenoxymethyl, R12 is hydrogen, C1-C12 alkyl, -COR10 or-CON(R8)(R9), R8, Rg and R10 being as defined above and R13 is C1-C12 alkyl, phenyl or C7-C14 alkaryl, and ii) a phenolic antioxidant.
2. A colour-photographic recording material according to claim 1, wherein, in the formula I, R1 is allyl, benzyl or a group
Figure imgb0111
Figure imgb0112
b is one of the numbers 0, 1 or 2, R7 is C1-C4 alkyl, allyl or benzyl, R8 is C1-C4 alkyl, allyl or cyclohexyl, Rg is C1-C12 alkyl or allyl, or R8 and Rg, together with the N atom to which they are linked, form a morpholine or piperidine radical, and R10 is C1-C12 alkyl, vinyl, cyclohexyl, benzyl or phenyl, R11 is hydrogen, methyl or phenyl and R12 is hydrogen, methyl or a group -CON(R8)(Rg), R8 and Rg being as already defined in this claim.
3. A colour-photographic recording material according to claim 1, which contains, as the component i), a component of the formula II
Figure imgb0113
in which n is one of the numbers 1 to 4, R and R1 are as defined for claim 1 and, if n = 1, R14 is hydrogen, C1-C12 alkyl, cyanoethyl, benzyl, glycidyl, a monovalent radical of a saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid, carbamic acid or phosphorous-containing acid or a monovalent silyl radical or, if n = 2, R14 is C2-C12 alkylene, C4-C8 alkenylene, xylylene, a divalent radical of a saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical or, if n = 3, R14 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical or, if n = 4, R14 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
4. A colour-photographic recording material according to claim 3, wherein, in the compound of the formula II, n is the number 1 or 2 and R14, if n = 1, is a radical of an aliphatic carboxylic acid having 2-18 C-atoms, a cycloaliphatic carboxylic acid having 5-12 C atoms or an aromatic carboxylic acid having 7-15 C atoms or, if n = 2, is a radical of an aliphatic dicarboxylic acid having 2-12 C atoms, a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C atoms.
5. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula III
Figure imgb0114
in which c is the number 1 or 2, R and R1 are as defined in claim 1, R15 is C1-C12 alkyl, C5-C8 cycloalkyl, C7-C8 aralkyl, C2-C18 alkynoyl or benzoyl and, if c = 1, R16 is C1-C12 alkyl, C5-C8 cycloalkyl, C2-CB alkenyl which is unsubstituted or substituted by a cyano group, carbonyl group or carbamide group, glycidyl, a group of the formulae -CHz-CH(OH)-Z, -COO-Z or-CONH-Z, in which Z is hydrogen, methyl or phenyl, and, if c = 2, R16 is C2-C12 alkylene, C6-C12 arylene, xylylene, a group -CHz-CH(OH)-CHz- or a group -CH2CH(OH)-CH2-O-X-O-CH2CH(OH)-CH2-, in which X is C2-C10 alkylene, C6-C15 arylene or C6-C12 cycloalkylene, or, provided that R15 is not alkanoyl, alkenoyl or benzoyl, R16 can also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or, if c = 1, R15 and R16 together can be the cyclic radical of an aliphatic or an aromatic 1,2- or 1,3-dicarboxylic acid.
6. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula IV
Figure imgb0115
in which R and R1 are as defined in claim 1 and W is one of the groups
Figure imgb0116
Figure imgb0117
in which R17 is hydrogen, C1-C12 alkyl, a group -CHz-OCOR22, wherein R22 is hydrogen, C1-C4 alkyl, C2-C6 alkenyl, cyclohexyl, phenyl, benzyl or chloromethyl, a group -CH2O-S(O)qR23, wherein R23 is C1-C4 alkyl, p-tolyl or phenyl and q is the number 1 or 2, where R17 is a group -CH2-OCO-NHR24 wherein R24 is hydrogen or C1-C4 alkyl, R18 is hydrogen or C1-C4 alkyl, R19 is hydrogen, C1-C12 alkyl, C3-C4 alkoxyalkyl, C6-C8 cycloalkyl, allyl or benzyl, R20 is hydrogen, C1-C12 alkyl, C5-C8 cycloalkyl or benzyl, R21 is C1-C12 alkyl, C5-C8 cycloalkyl or phenyl or R20 and R21, together with the C atom to which they are linked, form a C5-C12 cycloalkane or alkylcycloalkane ring, and W can additionally also be one of the groups of the formulae
Figure imgb0118
Figure imgb0119
or
Figure imgb0120
in which g is one of the numbers 1 to 12.
7. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula V
Figure imgb0121
in which R and R1 are as defined in claim 1 and R25 is a group CrH2r, in which r is a number from 2 to 12, or C4-C8 alkenylene, C4-C8 alkynylene, phenylene, xylylene, bitolylene, C5-C12 cycloalkylene or a group -CH2CH(OY)CH2-(OCH2-CH(OY)CH2)2-, wherein Y is hydrogen, C1-C18 alkyl, allyl, benzyl, C2-C12 alkanoyl or benzoyl, or R25 is a group -CONH-B-NHCO-, wherein B is a group CrH2r, phenylene, naphthylene, tolylene or a group of the formulae
Figure imgb0122
or
Figure imgb0123
in which R26 is hydrogen or methyl and R27 is hydrogen, methyl or ethyl.
8. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula VI
Figure imgb0124
in which d is the number 1 or 2 and R28 is a group of the formula
Figure imgb0125
in which R and R1 are as defined in claim 1, Q is -0- or -N(R31)-, A is C2-C6 alkylene and m is the number 0 or 1, R29 is one of the groups R28, -NR31R32, -OR33, -NHCH2OR33 or-N(CH2OR33)2, R30 is, if d = 1, one of the groups R28 or R29 and, if d = 2, is the group -Q-D-Q-, in which D is Cz-C6 alkylene which is uninterrupted or is interrupted by -N(R34)-, R31 is hydrogen, C1-C12 alkyl, allyl, cyclohexyl, benzyl or C1-C4 hydroxyalkyl or a group of the formula
Figure imgb0126
R32 is C1-C12 alkyl, allyl, cyclohexyl, benzyl or C1-C4 hydroxyalkyl, R33 is C1-C12 alkyl or phenyl and R34 is hydrogen or the group -CH20R33, or R31 and R32 together are C4-C5 alkylene or oxaalky- lene, or R31 and R32 can also each be a group of the formula
Figure imgb0127
9. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula VII
Figure imgb0128
in which e is the number 1 or 2, R is hydrogen or methyl and R35 is, if e = 1, C4-C18 alkyl, C7-C12 aralkyl, the group -CO-R36 or C1-C4 alkyl substituted by -CN, -COOR37, -OH, -OCOR38 or
Figure imgb0129
in which R36 is C1-C12 alkyl, C2-C4 alkenyl or phenyl, R37 is C1-C18 alkyl, R38 is C1-C18 alkyl, C2-C10 alkenyl, cyclohexyl, benzyl or C6-C10 aryl, or, if e = 2, R35 is C4-C12 alkylene, but-2-en-1,4- ylene, xylylene, one of the groups
Figure imgb0130
Figure imgb0131
Figure imgb0132
R39 being C2-C10 alkylene, phenylene, cyclohexylene or 2,2-diphenylenepropane and R40 being C2-C10 alkylene, xylylene or cyclohexylene.
10. A colour-photographic recording material according to claim 1, which contains, as the component i), a polymeric compound selected from the group comprising polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly-(meth)acrylamides and copolymers thereof, the recurring structural units of which contain a group of the formula I or are linked via a bivalent group of the formula (I) in which R1 is a free valency, R and R1 in other respects being as defined in claim 1.
11. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula VIII
Figure imgb0133
in which R41 is a radical of the formula IX
Figure imgb0134
in which j is 1 or 2 and the radicals R and R1 are as defined in claim 1.
12. A colour-photographic recording material according to claim 1, which contains, as the component ii), a phenolic antioxidant selected from the group comprising
2,6-di-tert-butyl-4-methylphenol,
2,2'-methylene-bis-(6-tert-butyl-4-methylphenol),
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol),
4,4'-methylene-bis-(2,6-di-tert-butylphenol),
2,2-bis-(2,6-di-tert-butyl-4-hydroxyphenyl)-propane,
2,2'-methylene-bis-[4-methyl-6-(a-methylcyclohexyl)-phenol],
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,
ethylene glycol bis-[3,3-bis-(3-tert-butyl-4-hydroxyphenyl)-butyrate],
4,4'-thio-bis-(6-tert-butyl-3-methylphenol),
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
tri-ethylene glycol bis-(3-methyl-5-tert-butyl-4-hydroxyphenyl)-propionate,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylendiamine,
3-thia-1,5-pentanediol-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate],
1,6-hexanediol-bis-[3-(2,5-di-tert-butyl-4-hydroxyphenyl)-propionate],
pentaerythritol tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate],
pentaerythritol tetrakis-(3,5-di-tert-butyl-4-hydroxybenzoate),
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate,
2-(3,5-di-tert-butyl-4-hydroxyanilino)-4,6-di-(octylthio)-triazine,
2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, the phenol nf the formula XI
Figure imgb0135
or the phenol of the formula X
Figure imgb0136
13. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula C
Figure imgb0137
and, as the component ii), a compound of the formula a
Figure imgb0138
14. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula A
Figure imgb0139
and, as the component ii), a compound of the formula b
Figure imgb0140
15. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula t
Figure imgb0141
and, as the component ii), a compound of the formula c
Figure imgb0142
16. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula E
Figure imgb0143
and, as the component ii), a compound of the formula d
Figure imgb0144
17. A colour-photographic recording material according to claim 1, which contains, as the component i), a compound of the formula D
Figure imgb0145
and, as the component ii), a compound of the formula e
Figure imgb0146
18. A colour-photographic recording material according to claim 1, which contains the stabiliser mixture i) + ii) in combination with cyan, magenta and yellow couplers.
19. A colour-photographic recording material according to claim 1, which contains the stabiliser mixture i) + ii) in combination with ultraviolet absorbers.
20. A colour-photographic recording material according to claim 19, wherein the ultraviolet absorbers are compounds of the benzophenone, acrylonitrile, thiazolidone, benzotriazole, oxazole, thiazole or imidazole types.
21. A colour-photographic recording material according to claim 1, which contains the stabiliser mixture i) and ii) in combination with cyan, magenta and yellow couplers and with ultraviolet absorbers in the same layer.
22. A colour-photographic recording material according to claim 1, which contains 1 to 2,000 mg of the stabiliser mixture i) and ii) per m2 of the layer into which the stabiliser mixture is incorporated.
23. A process for the production of photographic colour images by imagewise exposure and colour development of the colour-photographic recording material according to claim 1.
EP83810582A 1982-12-16 1983-12-12 Colour-photographic recording material Expired EP0114028B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH731482 1982-12-16
CH7314/82 1982-12-16

Publications (3)

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EP0114028A2 EP0114028A2 (en) 1984-07-25
EP0114028A3 EP0114028A3 (en) 1985-12-27
EP0114028B1 true EP0114028B1 (en) 1988-08-03

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US (1) US4517283A (en)
EP (1) EP0114028B1 (en)
JP (1) JPS59116747A (en)
CA (1) CA1203410A (en)
DE (1) DE3377596D1 (en)

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JPH0653436B2 (en) * 1985-09-10 1994-07-20 キヤノン株式会社 Image protection member and image protection method
USH567H (en) 1985-11-21 1989-01-03 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive materials containing cyan coupler and specific compound
US4797350A (en) * 1986-04-16 1989-01-10 Konishiroku Photo Industry Co., Ltd. Process for forming dye-image using a developer comprising an image stabilizer, a hydroxylamine and not containing benzyl alcohol
DE3765765D1 (en) * 1987-01-16 1990-11-29 Agfa Gevaert Nv POLYMERS AS SEEDING AGENTS FOR ACID DYES.
US4859759A (en) * 1988-04-14 1989-08-22 Kimberly-Clark Corporation Siloxane containing benzotriazolyl/tetraalkylpiperidyl substituent
JP2909507B2 (en) * 1989-02-08 1999-06-23 富士写真フイルム株式会社 Silver halide color photographic materials
JPH052246A (en) * 1991-06-24 1993-01-08 Fuji Photo Film Co Ltd Silver halide color photosensitive material
JPH055975A (en) * 1991-06-28 1993-01-14 Konica Corp Silver halide photographic sensitive material
JP2681422B2 (en) * 1991-07-09 1997-11-26 富士写真フイルム株式会社 Silver halide color photographic materials
DE19515143A1 (en) * 1995-04-25 1996-10-31 Agfa Gevaert Ag Colour photographic material for avoiding reducing max. density
EP1493057A1 (en) * 2002-03-05 2005-01-05 Ciba SC Holding AG Colour photographic recording material
CN101558091B (en) * 2006-12-18 2013-03-27 3M创新有限公司 (meth)acrylic resin composition and films of same
JP4988383B2 (en) * 2007-03-02 2012-08-01 スリーエム イノベイティブ プロパティズ カンパニー (Meth) acrylic colored film, marking film, receptor sheet, and method for producing the same
JP5307378B2 (en) * 2007-10-26 2013-10-02 スリーエム イノベイティブ プロパティズ カンパニー (Meth) acrylic film and marking film using the same
KR100924010B1 (en) 2007-12-18 2009-10-28 제일모직주식회사 Photosensitive resin composition for color filter and color filter using same

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Publication number Publication date
DE3377596D1 (en) 1988-09-08
CA1203410A (en) 1986-04-22
US4517283A (en) 1985-05-14
US4517283B1 (en) 1992-04-28
EP0114028A2 (en) 1984-07-25
EP0114028A3 (en) 1985-12-27
JPS59116747A (en) 1984-07-05

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