EP0586974B1 - Silver halide colour photographic material - Google Patents

Description

The invention relates to a color photographic silver halide material based on a Carrier has at least one yellow-coupling silver halide emulsion layer and improved light stability of the generated by the processing Azomething yellow dye.

It is known to produce color photographic images by chromogenic development, i.e. by imagewise exposed silver halide emulsion layers in the presence of suitable color couplers using suitable color-forming developer substances - so-called color developer - developed, which in accordance Oxidation product of the developer substances with the silver image Color coupler reacts to form a dye image. Become a color developer usually aromatic compounds containing primary amino groups, especially those of the p-phenylenediamine type used.

It is also known that the image dyes produced by chromogenic development to varying degrees under the influence of environmental conditions Undergo changes. The influence of light is of particular influence. As is well known bleach those produced from the open chain ketomethylene compounds yellow azomethine dyes particularly strong, while the ones from phenolic or naphtholic couplers produced cyan dyes as fairly prove stable and the purple dyes produced from pyrazolone couplers by addition suitable light stabilizers in the meantime to the cyan couplers were approximated.

The object of the invention was therefore to improve the light stability of the yellow dyes, so that the longer exposure of light to color photos with initially balanced Colors do not cause uneven fading of the dyes, what that Would result in a color cast. The to improve light resistance The agents proposed for the purple dyes are for the stabilization of the Yellow dyes are only suitable to a limited extent and, moreover, often with others Disadvantages that they appear to be unsuitable for practical use to let. As hydroquinones or hydroquinone derivatives, they are easily oxidizable and often give rise to an undesirable coloring (yellowing) of the image whites. With longer storage, they are often caused by the action of atmospheric oxygen or other oxidizing agents oxidize and lose their effectiveness.

From GB-A-1 267 287 bisphenol compounds are known, both of which are phenolic OH groups are unsubstituted. These compounds are suitable as light stabilizers for yellow dyes, but the effect is still insufficient.

From EP-A-246 766 bisphenol compounds are known, in which a phenolic Hydroxyl group is substituted. These are not in their light stabilizing effect better than the free bisphenols of GB-A-1 267 287, but lead to minor purer shades.

It has now surprisingly been found that certain bisphenol derivatives with a substituted phenolic OH group the light stability of the yellow azomethine dyes improve significantly without affecting the color purity or a coloring of the image whites is found.

enthält, worin

R₉

gleich oder verschieden einen Rest

R₁₀

gleich oder verschieden eine Alkylgruppe, insbesondere mit 1 bis 9 C-Atomen,

R₁₁

H oder Alkyl,

R₁₂

H, Aryl oder Alkyl,

R₁₃

H, Aryl oder Alkyl,

R₁₄, R₁₅

gleich oder verschieden Alkyl, insbesondere mit 1 bis 4 C-Atomen,

R₁₆

H oder Alkyl, insbesondere mit 1 bis 4 C-Atomen bedeuten.

The invention relates to a color photographic material having at least one silver halide emulsion layer which comprises at least one compound of the formula (I)

contains what

R ₉

the same or different a rest

R ₁₀

an alkyl group, the same or different, in particular with 1 to 9 carbon atoms,

R ₁₁

H or alkyl,

R ₁₂

H, aryl or alkyl,

R ₁₃

H, aryl or alkyl,

R ₁₄ , R ₁₅

the same or different alkyl, in particular with 1 to 4 carbon atoms,

R ₁₆

H or alkyl, in particular with 1 to 4 carbon atoms.

The compounds of formula (I) can also be in oligomeric or polymeric form available.

With these connections there is already an improved stability of the yellow coupler reached. The yellow coupler can preferably be in an oligomeric or polymeric Oil formers should be distributed.

Oligomers or polymeric oil formers are soluble in organic solvents Compounds with a unit which is repeated at least twice in the molecule, whose boiling point is above 200 ° C, in which color couplers are dissolved or dispersed can be.

The two radicals R ₉ are preferably identical, likewise the two radicals R ₁₀ , R ₉ is preferably isopropyl, tert-butyl, cyclohexyl, tert-amyl and 1-methylcyclohexyl. R ₁₀ is preferably methyl, ethyl, propyl, isopropyl n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, nonyl.

R ₁₁ , R ₁₂ , R ₁₃ are in particular H or CH ₃ .

Verbindung R₁₀ R_10' R₁₁ R₁₂ I-1 C₂H₅ C₂H₅ H H I-2 t-C₄H₉ t-C₄H₉ H H I-3 n-C₄H₉ n-C₄H₉ H H I-4 CH₃ CH₃ H H I-5 C₉H₁₉ C₉H₁₉ H H I-6 C₂H₅ C₂H₅ CH₃ H I-7 CH₃ CH₃ CH₃ H I-8 CH₃ CH₃ H CH₃ I-9 CH₃ CH₃ H C₆H₅ I-10 t-C₄H₉ t-C₄H₉ CH₃ H sowie

Suitable examples are the following compounds

connection R ₁₀ R _{10 '} R ₁₁ R ₁₂ I-1 C ₂ H ₅ C ₂ H ₅ H H I-2 tC ₄ H ₉ tC ₄ H ₉ H H I-3 nC ₄ H ₉ nC ₄ H ₉ H H I-4 CH ₃ CH ₃ H H I-5 C ₉ H ₁₉ C ₉ H ₁₉ H H I-6 C ₂ H ₅ C ₂ H ₅ CH ₃ H I-7 CH ₃ CH ₃ CH ₃ H I-8 CH ₃ CH ₃ H CH ₃ I-9 CH ₃ CH ₃ H C ₆ H ₅ I-10 tC ₄ H ₉ tC ₄ H ₉ CH ₃ H such as

The bisphenol compounds are preferably used in an amount of 0.1 to 2 g / g Color couplers, especially used in an amount of 0.1 to 1 g / g color coupler.

The average molecular weight of the oligomeric or polymeric oil formers (Weight average) is preferably not greater than 200,000, preferably 400 to 100,000. The oligomeric or polymeric oil formers are preferably in one Amount of 0.05 to 10 g / g color coupler, especially in an amount of 0.1 to 4 g / g color coupler used.

1. Vinylpolymere und Copolymere, Acrylate, wie Methylacrylat, Ethylacrylat, Isopropylacrylat, Butylacrylat, t-Butylacrylat, Amylacrylat, Hexylacrylat, 2-Ethylhexylacrylat, t-Octylacrylat, Cyanoethylacrylat, 2-Acetoxyethylacrylat, Dimethylaminoethylacrylat, Methoxybenzylacrylat, Cyclohexylacrylat, Tetrahydrofurfurylacrylat, Phenylacrylat, 2,2-Dimethyl-3-hydroxypropylacrylat, 2-Methoxyethylacrylat, 2-Ethoxyethylacrylat, 2-Isopropoxyacrylat, 2-(2-Methoxyethoxy)-ethylacrylat; Methacrylate wie Methylmethacrylat, Ethylmethacrylat, Propylmethacrylat, Butylmethacrylat, Isobutylmethacrylat, Amylmethacrylat, Cyclohexylmethacrylat, Benzylmethacrylat, Octylmethacrylat, Sulfopropylmethacrylat, N-Ethyl-N-phenylaminoethylmethacrylat, Dimethylaminophenoxyethylmethacrylat, Furfurylmethacrylat, Glycidylmethacrylat, Phenylmethacrylat, Kresylmethacrylat, Naphthylmethacrylat, 2-Hydroxyethylmethacrylat, Triethylenglykolmethacrylat, 2-Methoxyethylmethacrylat, 2-Acetoxyethylmethacrylat, 2-Ethoxyethylmethacrylat, 2-(2-Methoxyethoxy)-ethylmethacrylat und ω-Methoxypolyethylenglykolmethacrylat, Vinylester wie Vinylacetat, Vinylpropionat, Vinylbutylat, Vinylisobutylat, Vinylcaproat, Vinylchloracetat, Vinylmethoxyacetat, Vinylphenylacetat, Vinylbenzoat und Vinylsalicylat; Acrylamide wie Acrylamid, Ethylacrylamid, Propylacrylamid, Butylacrylamid, t-Butylacrylat, Cyclohexylacrylamid, Benzylacrylamid, Hydroxymethylacrylamid, Methoxyethylacrylamid, Dimethylaminoethylacrylamid, Phenylacrylamid, Dimethylacrylamid, β-Cyanethylacrylamid, N-(2-Acetoxyethyl)-acrylamid und Diacetonacrylamid; Methacrylamide wie Methacrylamid, Methylmethacrylamid, Ethylmethacrylamid, Propylmethacrylamid, Butylmethacrylamid, t-Butylmethacrylamid, Cyclohexylmethacrylamid, Benzylmethacrylamid, Hydroxymethylmethacrylamid, Methoxyethylmethacrylamid, Dimethylaminoethylmethacrylamid, Phenylmethacrylamid, β-Cyanethylmethacrylamid und N-(2-Acetoacetoxyethyl)-methacrylamid; Olefine wie Dicyclopentadien, Ethylen, Propylen, 1-Buten, 1-Penten, Vinylchlorid, Vinylidenchlorid, Isopren, Chloropren, Butadien und 2,3-Di-methylbutadien; Styrole wie Styrol, Methylstyrol, Trimethylstyrol, Ethylstyrol, Chlormethylstyrol, Methoxystyrol, Chlorstyrol, Dichlorstyrol und Methylvinylbenzoat; Crotonate wie Butylcrotonat und Hexylcrotonat, Itaconate wie Dimethylitaconat und Dibutylitaconat; Maleate wie Diethylmaleat, Dimethylmaleat und Dibutylmaleat, Fumarate wie Diethylfumarat, Dimethylfumarat und Dibutylfumarat; Allylverbindungen wie Allylacetat, Allylcaproat, Allyllaurat und Allylbenzoat; Vinylether wie Methylvinylether, Butylvinylether, Methoxyethylvinylether und Dimethylaminoethylvinylether; Vinylketone wie Methylvinylketon, Phenylvinylketon und Methoxyethylvinylketon; heterocyclische Vinylverbindungen wie Vinylpyridin, N-Vinylimidazol, N-Vinyloxazolidon, N-Vinyltriazol und N-Vinylpyrrolidon; Glycidylester wie Glycidylacrylat und Glycidylmethacrylat; und ungesättigte Nitrile wie Acrylnitril und Methacrylnitril. Weiterhin können Harnstoff- undloder Urethangruppen aufweisende Monomere enthalten sein. Die polymeren Ölbildner können dabei Homopolymere der obengenannten Monomere oder Copolymere von zwei oder mehr der vorstehend genannten Monomere sein. Die Polymere können Monomere mit Säuregruppen in einer Menge enthalten, die sie nicht wasserlöslich macht. Beispiele für Monomere mit Säuregruppen sind Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure, Itaconsäuremonoalkylester, Maleinsäuremonoalkylester, Citraconsäure, Styrolsulfonsäure, Vinylbenzylsulfonsäure, Acryloyloxyalkylsulfonsäure, Methacryloyloxyalkylsulfonsäure, Acrylamidalkylsulfonsäure, Methacrylamidalkylsulfonsäure, Acryloyloxyalkylphosphat und Methacryloyloxyalkylphosphat. Diese Säuren können auch in Salzform mit einem Alkalimetall wie Natrium und Kalium oder mit einem Ammoniumion eingesetzt werden. Acrylate, Acrylamide und Methacrylate sind die bevorzugten Monomere zur Bildung der polymeren Ölformer dieser Erfindung. Die Polymere können durch Lösungspolymerisation, Massepolymerisation, Suspensionspolymerisation und Emulsionspolymerisation hergestellt werden.Die frei-radikalische Polymerisation eines ethylenisch ungesättigten Monomers wird initiiert durch Zusatz eines freien Radikals, das gebildet wird durch thermische Zersetzung eines chemischen Initiators, durch Einwirkung eines Reduktionsmittels auf eine oxidierende Verbindung (Redox-Initiator) oder durch physikalische Einwirkung, wie Bestrahlung mit Ultraviolettstrahlen oder anderen hochenergetischen Strahlungen, hohen Frequenzen, usw.Beispiele für chemische Initiatoren umfassen Persulfate (beispielsweise Ammoniumpersulfat oder Kaliumpersulfat, Wasserstoffperoxid, organische Peroxide (beispielsweise Benzoylperoxid oder t-Butylperoctoat) und Azonitrilverbindungen (beispielsweise 4,4'-Azobis-4-cyanovaleriansäure oder Azobisisobutyronitril).Beispiele für konventionelle Redox- Initiatoren umfassen Wasserstoffperoxid-Eisen(II)-salz, Kaliumpersulfat, Natriummetabisulfit und Cer-IV-Salz-Alkohol, usw.Beispiele für die Initiatoren und deren Funktionen werden beschrieben von F.A. Bovey, in Emulsion Polymerisation, Interscience Publishers Inc., New York, 1955, Seiten 59 bis 93.Als Emulgator, der bei der Emulsionspolymerisation verwendet werden kann, wird eine Verbindung mit oberflächenaktiver Wirkung verwendet. Bevorzugte Beispiele dafür umfassen Seife, ein Sulfonat, ein Sulfat, eine kationische Verbindung, eine amphotere Verbindung und ein Schutzkolloid mit hohem Molekulargewicht. Spezielle Beispiele für die Emulgatoren und deren Funktionen werden beschrieben in Belgische Chemische Industrie, Bd. 28, Seiten 16 bis 20, 1963.

2. Polyesterharze hergestellt durch Polykondensation eines mehrwertigen Alkohols und einer mehrbasischen Säure: Mehrwertige Alkohole sind Glykole mit einer Kohlenwasserstoffkette von 2 bis 12 Kohlenstoffatomen, insbesondere mit einer aliphatischen Kohlenwasserstoffkette oder Polyalkylenglykole. Mehrbasische Säuren sind Dicarbonsäuren, deren Carboxylgruppen durch eine Kohlenwasserstoffkette mit 1 bis 12 Kohlenstoffatome voneinander getrennt sind. Beispiele für mehrwertige Alkohole sind Ethylenglykol, Diethylenglykol, 1,2-Propylenglykol, 1,3-Propylenglykol, Trimethylolpropan, 1,4-Butandiol, Isobutylendiol, 1,5-Pentandiol, Neopentylglykol, 1,6-Hexandiol, 1,8-Octandiol, 1,9-Nonandiol, 1,10-Decandiol, Glycerin, Diglycerin, Triglycerin, 1-Methylglycerin, Pentaerythrit, Mannit und Sorbit. Beispiele für mehrbasische Säuren sind Oxalsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimellinsäure, Korksäure, Azelainsäure, Sebacinsäure, Decandicarbonsäure, Dodecandicarbonsäure, Fumarsäure, Maleinsäure, Itaconsäure, Citraconsäure, Phthalsäure, Isophthalsäure, Terephthalsäure, Tetrachlorphthalsäure, Metaconsäure, Isopimellinsäure und das Addukt aus Cyclopentadien und Maleinsäureanhydrid.

3. Polyester hergestellt durch ringöffnende Polykondensation Diese Polyester werden von β-Propiolacton, α-Caprolacton und Dimethylpropiolacton hergestellt.

4. Andere Polymere Polycarbonate hergestellt durch Polykondensation eines Glykols oder Bisphenols mit einem Kohlensäureester oder Phosgen, Polyurethanharze hergestellt durch Polyaddition eines polymeren Alkohols mit einem Polyisocyanat und Polyamidharze hergestellt durch Polykondensation eines mehrwertigen Amins und einer mehrbasischen Säure, Phenolaldehydharze, die durch Polykondensation von Phenolen und Aldehyd hergestellt werden;
Alkylenoxidadditionsprodukte von Phenolaldehydharzen, Polyadditionsprodukte von Alkylenoxiden; Polyepoxide, die durch Umsetzung von Bisphenolen, Alkoholen, Diaminen oder schwefelhaltigen Verbindungen (wie Dithiophenole), Phenolaldehyd-Harzen, Polyalkoholen, Polycarbonsäuren, Polyaminen mit Epihalogenhydrin (z.B. Epichlorhydrin) oder aus Polyisocyanaten und Glycid erhalten werden.

Examples of oligomeric and polymeric oil formers of the present invention include the following:

1. Vinyl polymers and copolymers, acrylates, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, t-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, t-octyl acrylate, cyanoethyl acrylate, phenyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, , 2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-isopropoxyacrylate, 2- (2-methoxyethoxy) ethyl acrylate; Methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, glycidyl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, Triethylenglykolmethacrylat, 2- Methoxyethyl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate and ω-methoxypolyethylene glycol methacrylate, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butylate, vinyl isobutylate, vinyl caproate, vinyl chloroacetate, vinylphenylacetate, vinylphenylacetate; Acrylamides such as acrylamide, ethyl acrylamide, propylacrylamide, butylacrylamide, t-butyl acrylate, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, β-cyanoethylacrylamide and diacylacrylamide, Methacrylamides such as methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, β-cyanoethyl methacrylamide and N- (2-acetaminomethacylamide); Olefins such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene and 2,3-dimethylbutadiene; Styrenes such as styrene, methylstyrene, trimethylstyrene, ethylstyrene, chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene and methylvinylbenzoate; Crotonates such as butyl crotonate and hexyl crotonate, itaconates such as dimethyl itaconate and dibutyl itaconate; Maleates such as diethyl maleate, dimethyl maleate and dibutyl maleate, fumarates such as diethyl fumarate, dimethyl fumarate and dibutyl fumarate; Allyl compounds such as allyl acetate, allyl caproate, allyl laurate and allyl benzoate; Vinyl ethers such as methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether; Vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone and methoxyethyl vinyl ketone; heterocyclic vinyl compounds such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole and N-vinylpyrrolidone; Glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; and unsaturated nitriles such as acrylonitrile and methacrylonitrile. Monomers containing urea and / or urethane groups may also be present. The polymeric oil formers can be homopolymers of the abovementioned monomers or copolymers of two or more of the abovementioned monomers. The polymers can contain monomers with acid groups in an amount that does not render them water-soluble. Examples of monomers with acid groups are acrylic acid, methacrylic acid, itaconic acid, maleic acid, itaconic acid monoalkyl esters, maleic acid monoalkyl esters, citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid, acryloyloxyalkylsulfonic acid, methacryloyloxyalkylsulfonic acid, acrylamidalkylsulfonic acid and methacrylamidealkylloxyphosphate, methacrylamide alkylsulfoyl phosphate. These acids can also be used in salt form with an alkali metal such as sodium and potassium or with an ammonium ion. Acrylates, acrylamides and methacrylates are the preferred monomers for forming the polymeric oil formers of this invention. The polymers can be prepared by solution polymerization, bulk polymerization, suspension polymerization and emulsion polymerization. The free radical polymerization of an ethylenically unsaturated monomer is initiated by adding a free radical, which is formed by thermal decomposition of a chemical initiator, by the action of a reducing agent on an oxidizing compound ( Redox initiator) or by physical action such as irradiation with ultraviolet rays or other high-energy radiation, high frequencies, etc. Examples of chemical initiators include persulfates (e.g. ammonium persulfate or potassium persulfate, hydrogen peroxide, organic peroxides (e.g. benzoyl peroxide or t-butyl peroctoate) and azonitrile compounds ( for example 4,4'-azobis-4-cyanovaleric acid or azobisisobutyronitrile). Examples of conventional redox initiators include hydrogen peroxide iron (II) salt, potassium persu lfat, sodium metabisulfite and cerium IV salt alcohol, etc. Examples of the initiators and their functions are described by FA Bovey, in Emulsion Polymerization, Interscience Publishers Inc., New York, 1955, pages 59 to 93 can be used in the emulsion polymerization, a compound having a surface active effect is used. Preferred examples thereof include soap, a sulfonate, a sulfate, a cationic compound, an amphoteric compound and a high molecular weight protective colloid. Specific examples of the emulsifiers and their functions are described in Belgische Chemische Industrie, vol. 28, pages 16 to 20, 1963.

2. Polyester resins produced by polycondensation of a polyhydric alcohol and a polybasic acid: polyhydric alcohols are glycols with a hydrocarbon chain of 2 to 12 carbon atoms, in particular with an aliphatic hydrocarbon chain or polyalkylene glycols. Polybasic acids are dicarboxylic acids whose carboxyl groups are separated from each other by a hydrocarbon chain with 1 to 12 carbon atoms. Examples of polyhydric alcohols are ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylenediol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol, 1,8-octanediol , 1,9-nonanediol, 1,10-decanediol, glycerol, diglycerol, triglycerol, 1-methylglycerol, pentaerythritol, mannitol and sorbitol. Examples of polybasic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimellic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalenedioic acid, from terephthalenedic acid, from terephthalic acid phthalic acid, from terephthalic acid phthalic acid, from terephthalic acid phthalic acid from terephthalic acid phthalic acid Maleic anhydride.

3. Polyesters made by ring-opening polycondensation These polyesters are made from β-propiolactone, α-caprolactone and dimethylpropiolactone.

4. Other polymers polycarbonates made by polycondensation of a glycol or bisphenol with a carbonic acid ester or phosgene, polyurethane resins made by polyaddition of a polymeric alcohol with a polyisocyanate and polyamide resins made by polycondensation of a polyvalent amine and a polybasic acid, phenol aldehyde resins made by polycondensation of phenols and aldehyde getting produced;
Alkylene oxide addition products of phenol aldehyde resins, polyaddition products of alkylene oxides; Polyepoxides which are obtained by reacting bisphenols, alcohols, diamines or sulfur-containing compounds (such as dithiophenols), phenol aldehyde resins, polyalcohols, polycarboxylic acids, polyamines with epihalohydrin (eg epichlorohydrin) or from polyisocyanates and glycid.

worin

R₉ und R₁₀

Alkyl

R₁₁

Wasserstoff oder Alkyl

X

-CH₂-CH₂- oder

R₁₂

Alkyl

o

1 bis 10

p

0 bis 20

bedeuten.Preferred oligomeric and polymeric oil formers correspond to the formula (III)

wherein

R ₉ and R ₁₀

Alkyl

R ₁₁

Hydrogen or alkyl

X

-CH ₂ -CH ₂ - or

R ₁₂

Alkyl

O

1 to 10

p

0 to 20

mean.

R ₉ is preferably hydrogen and R _{10 is} a C ₁ -C ₁₂ -alkyl radical which is in particular p-permanent to the oxygen.

R ₁₁ is especially hydrogen; R ₁₂ is especially methyl; o is in particular 1 to 5; p is in particular 0 to 5.

Examples of preferred oligomeric and polymeric oil formers are polymers with the following structural units

The preferred oligomeric and polymeric oil formers are obtained by adding Alkylene oxides produced on phenol adlehyd resins.

The compounds according to the invention are preferred in combination with yellow couplers used.

Dye stabilization is also possible with other couplers, magenta and cyan couplers of the photographic materials.

Examples of color photographic materials are color negative films, color reversal films, Color positive films, color photographic paper, color reversal photographic paper, color sensitive Materials for the color diffusion transfer process or the silver color bleaching process.

Suitable carriers for the production of color photographic Materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, Cellulose acetate, cellulose butyrate, polystyrene, Polyvinyl chloride, polyethylene terephthalate and polycarbonate and with a baryta layer or α-olefin polymer layer (e.g. polyethylene) laminated paper. These carriers can be mixed with dyes and pigments, for example titanium dioxide. You can also colored black for the purpose of shielding light be. The surface of the carrier is generally subjected to a treatment to improve the adhesion of the to improve photographic emulsion layer, for example a corona discharge with subsequent Application for a substrate layer.

It is preferably a color photographic one Paper with a polyethylene laminated on both sides Paper as a carrier.

The color photographic materials usually contain at least one red sensitive, green sensitive and blue sensitive silver halide emulsion layer and optionally intermediate layers and Protective layers.

Essential components of the photographic emulsion layers are binders, silver halide grains and Color coupler.

Gelatin is preferably used as the binder. However, this can be done in whole or in part by others synthetic, semi-synthetic or also naturally occurring Polymers to be replaced. Synthetic gelatin substitutes Examples include polyvinyl alcohol, poly-N-vinyl pyrrolidone, Polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example other proteins like albumin or casein, Cellulose, sugar, starch or alginates. Semi-synthetic Gelatin substitutes are usually modified Natural products. Cellulose derivatives such as hydroxyalkyl cellulose, Carboxymethyl cellulose and phthalyl cellulose as well as gelatin derivatives, which by implementation with alkylating or acylating agents or by Grafting polymerizable monomers obtained are examples of this.

The binders should have a sufficient amount of functional groups so that by implementation sufficiently resistant with suitable hardening agents Layers can be created. Such functional Groups are especially amino groups, but also Carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be acidic or alkaline digestion. It can also oxidized gelatin can be used. The production such gelatin is described, for example, in The Science and Technology of Gelatin, edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. described. The gelatin used in each case should have the lowest possible content of contain photographically active impurities (inert gelatin). Gelatins with high Viscosity and low swelling are particularly advantageous.

The one found in the photographic material as a light-sensitive component Silver halide can be used as halide, chloride, bromide or iodide or mixtures of which included. For example, the halide content can be at least one layer 0 to 15 mol% from iodide, 0 to 100 mol% from chloride and 0 to 100 mol% insist on bromide. The silver halide emulsions preferably consist of at least 80 mol% of material according to the invention from AgCl. In the case of color negative and color reversal films are usually silver bromoiodide emulsions, usually silver chloride bromide emulsions in the case of color negative and color reversal paper with a high chloride content up to pure silver chloride emulsions. It can be predominantly compact crystals, e.g. regular cubic or are octahedral or can have transitional forms. Preferably can also be platelet-shaped crystals, their average ratio from diameter to thickness is preferably at least 5: 1, the diameter a grain is defined as the diameter of a circle with a circle content according to the projected area of the grain. The layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly larger than 5: 1, e.g. 12: 1 to 30: 1.

The silver halide grains can also be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as Endowments of the individual Grain areas are different. The middle The grain size of the emulsions is preferably between 0.2 µm and 2.0 µm, the grain size distribution can be both be homo- and heterodisperse. Homodisperse grain size distribution means 95% of the grains are not deviate more than ± 30% from the average grain size. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.

Two or more types of silver halide emulsions, which are made separately, as a mixture be used.

The photographic emulsions can be different Methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) soluble silver salts and soluble halides will.

The silver halide is preferably precipitated in Presence of the binder, e.g. the gelatin and can carried out in the acidic, neutral or alkaline pH range are, preferably silver halide complexing agents can also be used. The latter belong e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The merge the water-soluble silver salts and the halides optionally takes place one after the other after the single-jet or simultaneously using the double-jet process or by any combination of both methods. Prefers the dosage becomes with increasing inflow rates, where the "critical" feed rate at which just no new germs are emerging, not exceeded should be. The pAg range can be changed during the Precipitation can vary within wide limits, preferably uses the so-called pAg-controlled method, in which a certain pAg is kept constant or on Run through the defined pAg profile during the precipitation becomes. In addition to the preferred precipitation with excess halide is also the so-called inverse Precipitation possible with excess of silver ions. Except through The silver halide crystals can also be precipitated by physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent to grow. The growth of the emulsion grains can even predominantly through Ostwald ripening take place, preferably a fine-grained, so-called Lippmann emulsion, with a less soluble Emulsion mixed and redissolved on the latter.

During precipitation and / or physical ripening The silver halide grains can also contain salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe to be available.

The precipitation can also be carried out in the presence of sensitizing dyes respectively. Complexing agent and / or dyes can be any Deactivate the point in time, e.g. by changing the pH or by an oxidative treatment.

After crystal formation is complete or already closed the soluble salts are removed at an earlier point in time removed from the emulsion, e.g. by pasta and washing, by flaking and washing, by ultrafiltration or through ion exchangers.

The silver halide emulsion generally becomes one chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until it is reached of the optimum sensitivity and fog. The procedure is e.g. with H. Frieser "The basics of the photographic processes with silver halides " Pages 675-734, Academic Publishing Company (1968).

The chemical sensitization can add of compounds of sulfur, selenium, tellurium and / or Compounds of metals of subgroup VIII Periodic table (e.g. gold, platinum, palladium, iridium) can take place, furthermore thiocyanate compounds, surface-active Compounds such as thioethers, heterocyclic Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described e.g. with F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III) can be added. Alternatively or in addition, a reduction sensitization with the addition of reducing agents (tin-II salts, Amines, hydrazine derivatives, aminoboranes, silanes, Formamidine sulfinic acid) by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8) be carried out.

The photographic emulsions can be compounds to Prevention of fog or for stabilization the photographic function during production, the Storage or photographic processing included.

Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.

The stabilizers can the silver halide emulsions before, during or after their ripening. Of course, the connections can also be made to others photographic layers that are a layer of halogen silver are assigned.

Mixtures of two or more of the above can also be used Connections are used.

The photographic emulsion layers or other hydrophilic Colloid layers of the one produced according to the invention Photosensitive material can be surface active Contain funds for various purposes, such as coating aids, to prevent electrical charging Improvement of the sliding properties, for emulsifying the Dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. Saponin, mainly synthetic surface-active compounds (surfactants) Use: non-ionic surfactants, e.g. Alkylene oxide compounds, Glycerin compounds or glycidol compounds, cationic Surfactants, e.g. higher alkylamines, quaternary ammonium salts, Pyridine compounds and other heterocyclic Compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing one Acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and Aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.

The photographic emulsions can be made using spectral of methine dyes or other dyes be sensitized. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex Merocyanine dyes.

An overview of those suitable as spectral sensitizers Polymethine dyes, their suitable combinations and super-sensitizing combinations contains Research Disclosure 17643 (Dec. 1978), chapter IV.

1. als Rotsensibilisatoren 9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa- bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.

2. als Grünsensibilisatoren 9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.

3. als Blausensibilisatoren symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

The following dyes, sorted by spectral range, are particularly suitable:

1. as red sensitizers 9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or selenecarbocyanine and 9-ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.

2. as green sensitizers 9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups and benzimidazocarbocyanines, which may also be further substituted and must also contain at least one sulfoalkyl group on the heterocyclic nitrogen.

3. As blue sensitizers, symmetrical or asymmetrical benzimidazo-, oxa-, thia- or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.

The differently sensitized emulsion layers become non-diffusing monomeric or polymeric color couplers assigned which is in the same shift or in a layer adjacent to it. Usually, the red-sensitive layers become cyan couplers, the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers assigned.

Color coupler for generating the blue-green partial color image are usually couplers of the phenol or α-naphthol type. Color coupler for the generation of the purple Partial color images are usually couplers of the type of 5-pyrazolones, indazolone or pyrazoloazoles. Color coupler for generating the yellow partial color image are usually couplers with an open chain ketomethylene grouping, in particular couplers of the type α-Acylacetamids, for example α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.

Y-1:

R¹ = -C₄H₉-t;

Y-2:

R¹ = -C₄H₉-t;

R⁵ = -SO₂NHCH₃

Y-3:

R¹ = -C₄H₉-t;

R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃

Y-4:

R¹ = -C₄H₉-t;

R⁴ = H; R⁵ = = -COOC₁₂H₂₅

Y-5:

R¹ = -C₄H₉-t;

Y-6:

R¹ = -C₄H₉-t;

Y-7:

R¹ = -C₄H₉-t;

R⁴ = = H; R⁵ = -NHSO₂-C₁₆H₃₃

Y-8:

R¹ = -C₄H₉-t;

Y-9:

R¹ = -C₄H₉-t;

R⁴ = H; R⁵ = -SO₂NHCOC₂H₅

Y-10:

R¹ = -C₄H₉-t;

Y-11:

R¹ = -C₄H₉-t;

Y-12:

R¹ = -C₄H₉-t;

Y-13:

R¹ = -C₄H₉-t;

R⁵ = -SO₂NHCH₃

Y-14:

R¹ = -C₄H₉-t;

Y-15:

R², R⁴, R⁵ = H; R³ = -OCH₃

Y-16:

R³, R⁵ = -OCH₃; R⁴ = H

Y-17:

R³ = Cl; R⁴ = = H; R⁵ = -COOC₁₂H₂₅

Y-18:

R³ = Cl; R⁴, R⁵ = -OCH₃

Y- 19:

R³ = -OCH₃; R⁴ = H; R⁵ = -SO₂N(CH₃)₂

Y-20:

R³ = -OCH₃; R⁴ = H;

Y-21:

Suitable yellow couplers include the following:

Y-1:

R ¹ = -C ₄ H ₉ -t;

Y-2:

R ¹ = -C ₄ H ₉ -t;

R ⁵ = -SO ₂ NHCH ₃

Y-3:

R ¹ = -C ₄ H ₉ -t;

R ⁴ = H; R ⁵ = -NHSO ₂ -C ₁₆ H ₃₃

Y-4:

R ¹ = -C ₄ H ₉ -t;

R ⁴ = H; R ⁵ = = -COOC ₁₂ H ₂₅

Y-5:

R ¹ = -C ₄ H ₉ -t;

Y-6:

R ¹ = -C ₄ H ₉ -t;

Y-7:

R ¹ = -C ₄ H ₉ -t;

R ⁴ = = H; R ⁵ = -NHSO ₂ -C ₁₆ H ₃₃

Y-8:

R ¹ = -C ₄ H ₉ -t;

Y-9:

R ¹ = -C ₄ H ₉ -t;

R ⁴ = H; R ⁵ = -SO ₂ NHCOC ₂ H ₅

Y-10:

R ¹ = -C ₄ H ₉ -t;

Y-11:

R ¹ = -C ₄ H ₉ -t;

Y-12:

R ¹ = -C ₄ H ₉ -t;

Y-13:

R ¹ = -C ₄ H ₉ -t;

R ⁵ = -SO ₂ NHCH ₃

Y-14:

R ¹ = -C ₄ H ₉ -t;

Y-15:

R ² , R ⁴ , R ⁵ = H; R ³ = -OCH ₃

Y-16:

R ³ , R ⁵ = -OCH ₃ ; R ⁴ = H

Y-17:

R ³ = Cl; R ⁴ = = H; R ⁵ = -COOC ₁₂ H ₂₅

Y-18:

R ³ = Cl; R ⁴ , R ⁵ = -OCH ₃

Y- 19:

R ³ = -OCH ₃ ; R ⁴ = H; R ⁵ = -SO ₂ N (CH ₃ ) ₂

Y-20:

R ³ = -OCH ₃ ; R ⁴ = H;

Y-21:

The color couplers can be 4-equivalent couplers, but also act as 2-equivalent couplers. Latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off at the clutch. To the 2 equivalent couplers colorless ones are to be expected are, as well as those that have an intense intrinsic color have, which disappears with the color coupling or replaced by the color of the image dye generated becomes (mask coupler), and the white couplers that react with color developer oxidation products essentially result in colorless products. To the 2 equivalent couplers such couplers are also to be expected, which in the Coupling point contain a removable residue that when reacting with color developer oxidation products in Freedom is set, either directly or after one or several other groups have been split off (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic Effectiveness unfolds, e.g. as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

DIR couplers, the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416. Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess are with such DIR couplers to achieve, e.g. the development inhibitor not immediately as a result of coupling with one split off oxidized color developer, but only after a further follow-up reaction, for example with a timing group is reached. Examples of this are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-0 157 146 and 0 204 175, in US-A-4 146 396 and 4,438,393 and in GB-A-2,072,363.

DIR couplers that release a development inhibitor which in the developer bath is essentially photographically ineffective Products are decomposed, for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713 described. With this measure, a trouble-free Development and processing consistency achieved.

When using DIR couplers, especially those that split off a diffusible development inhibitor, can be taken by taking suitable measures at the optical sensitization improvements in color rendering, e.g. a more differentiated color rendering, achieve, such as in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.

The DIR couplers can be used in a multi-layer photographic Material added to different layers e.g. also light-insensitive or intermediate layers. However, they are preferably the photosensitive silver halide emulsion layers added, the characteristic properties the silver halide emulsion, e.g. their iodide content, the Structure of the silver halide grains or their grain size distribution of influence on the photographic achieved Properties are. The influence of the released Inhibitors can be installed, for example an inhibitor scavenger layer according to DE-A-24 31 223 limited will. For reactivity or stability reasons it may be advantageous to use a DIR coupler the one in the respective layer in which it is introduced is one of those to be generated in this layer Color deviates from the color of the coupling.

To increase sensitivity, contrast and DAR or FAR couplers can achieve maximum density be used, which is a development accelerator or split off an fogger. links of this type are described, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087, 0 147 765 and in U.S.-A-4,618,572 and 4,656,123.

As an example for the use of BAR couplers (Bleach Accelerator Releasing Coupler) is on EP-A-193 389 referred.

It can be beneficial to combine the effects of one Coupler split off photographically effective group by modifying an intermolecular reaction this group after their release with a another group according to DE-A-35 06 805.

As with the DIR, DAR or FAR couplers mainly the effectiveness of the released at the clutch The rest is desirable and it is less on the color-forming Properties of these couplers are well received DIR, DAR or FAR couplers suitable for the Coupling result in essentially colorless products (DE-A-15 47,640).

The detachable residue can also be a ballast residue, see above that in the reaction with color developer oxidation products Coupling products are obtained that are diffusible are or at least a weak or restricted one Have mobility (US-A-4 420 556).

The material can still be different from couplers Contain compounds which contain, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, an fogger or a Free antifoggants, for example so-called DIR hydroquinones and other compounds, as for example in US-A-4 636 546, 4,345,024, 4,684,604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438 are described. This Connections perform the same function as the DIR, DAR or FAR couplers, except that they are not coupling products form.

High molecular weight color couplers are for example in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211 described. The high molecular color couplers are used in usually by polymerization of ethylenically unsaturated monomeric color couplers. You can but also obtained by polyaddition or polycondensation will.

Incorporation of couplers or other connections in silver halide emulsion layers can in the way done that first of the connection in question a solution, a dispersion or an emulsion and then the pouring solution for that one Layer is added. Choosing the right solution or dispersant depends on the particular Solubility of the compound.

Methods of introducing into water essentially are insoluble compounds by grinding processes for example in DE-A-26 09 741 and DE-A-26 09 742 described.

Hydrophobic compounds can also be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Appropriate methods are for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers Find.

The compounds can also be in the form of loaded latices be introduced into the casting solution. Is referred for example on DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130,115, U.S. 4,291,113.

The diffusion-resistant storage of anionic water-soluble Compounds (e.g. from dyes) can also be used With the help of cationic polymers, so-called pickling polymers respectively.

Suitable oil formers are e.g. Alkyl phthalate, Phosphonic acid esters, phosphoric acid esters, citric acid esters, Benzoic acid esters, amides, fatty acid esters, trimesic acid esters, Alcohols, phenols, aniline derivatives and Hydrocarbons.

Examples of suitable oil formers are dibutyl phthalate, Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridecyl phosphate, tributoxyethyl phosphate, Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, Diethyldodecanamide, N-tetradecylpyrrolidone, Isostearyl alcohol, 2,4-di-t-amylphenol, Dioctyl acylate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5-t-octylaniline, Paraffin, dodecylbenzene and diisopropylnaphthalene.

According to the invention contains at least one silver halide emulsion layer one distributed in a polymeric oil former Coupler in combination with a connection of the Formula (I).

Each of the differently sensitized, photosensitive Layers can consist of a single layer or two or more partial silver halide emulsion layers include (DE-C-1 121 470). Are there red sensitive silver halide emulsion layers Layer supports are often arranged closer than green-sensitive ones Silver halide emulsion layers and these again closer than blue-sensitive, whereby in general between green sensitive layers and blue sensitive layers a non light sensitive yellow filter layer.

With a suitably low intrinsic sensitivity of the green or Red sensitive layers can be avoided the yellow filter layer choose other layer arrangements, where on the carrier e.g. the blue sensitive, then the red sensitive and finally the green-sensitive layers follow.

The usually different between layers Spectral sensitivity arranged non-photosensitive Intermediate layers can contain agents which is an undesirable diffusion of developer oxidation products from a photosensitive to a other photosensitive layer with different prevent spectral sensitization.

Appropriate agents that include scavengers or EOP scavengers are mentioned in Research Disclosure 17,643 (Dec. 1978), Chapter VII, 17,842 (Feb. 1979) and 18,716 (Nov. 1979), page 650 and in EP-A-0 069 070, 0 098 072, 0 124 877, 0 125 522.

If there are several sub-layers of the same spectral sensitization before, so these can look at their Composition, especially what type and amount of silver halide grains concerns differentiate. In general becomes the sub-layer with higher sensitivity be arranged further away from the support than the partial layer with less sensitivity. Sub-layers same spectral sensitization can each other adjacent or through other layers, e.g. by Separate layers of other spectral sensitization be. For example, all highly sensitive and all low-sensitivity layers to form a layer package be summarized (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.

Compounds that absorb UV light are said to be on the one hand the image dyes before fading by UV-rich Protect daylight and on the other hand as filter dyes the UV light in daylight during exposure absorb and thus improve the color rendering of a film. Usually for the two tasks Connections of different structures are used. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), Cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or Benzoxazole compounds (US-A-3 700 455).

Ultraviolet absorbing couplers (such as Cyan couplers of the α-naphthol type) and ultraviolet absorbing Polymers are used, these ultraviolet absorbents can be done by pickling in a special Layer fixed.

Include filter dyes suitable for visible light Oxonol dyes, hemioxonol dyes, styryl dyes, Merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, Hemioxonol dyes and merocyanine dyes used particularly advantageously.

Suitable whiteners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3 269 840 and in GB-A-852 075 and 1 319 763 described.

Certain layers of binder, especially that of Carrier most distant layer, but also occasionally Intermediate layers, especially if they during the manufacturing process the furthest from the wearer represent removed layer, can be photographically inert Contain particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).

The average particle diameter of the spacers is in particular in the range from 0.2 to 10 µm. The spacers are insoluble in water and insoluble in alkali or be alkali-soluble, the alkali-soluble generally in an alkaline development bath the photographic material are removed. Examples suitable polymers are polymethyl methacrylate, copolymers from acrylic acid and methyl methacrylate as well Hydroxypropylmethyl cellulose hexahydrophthalate.

Additives to improve the dye, coupler and White stability and to reduce the color fog (Research Disclosure 17,643 (Dec. 1978), Chapter VII) can belong to the following chemical substance classes: Hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, Spirochromanes, spiroindanes, p-alkoxyphenols, steric hindered phenols, gallic acid derivatives, Methylenedioxybenzenes, aminophenols, sterically hindered Amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds that have both a sterically hindered amine partial structure as well as a sterically hindered Have phenol partial structure in one molecule (US-A-4 268 593), are particularly effective in preventing the Impairment of yellow color images as a result of Development of heat, moisture and light. To the Impairment of purple color images, in particular their impairment as a result of exposure to prevent light are spiroindanes (JP-A-159 644/81) and chromanes, which are mono-or by alkoxy groups are disubstituted (JP-A-89 835/80), especially effective.

The layers of the photographic material can with the usual hardening agents are hardened. Suitable Hardening agents are e.g. Formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and others Compounds containing reactive halogen (US-A-3 288,775, US-A-2,732,303, GB-A-974,723 and GB-A-1 167 207), divinyl sulfone compounds, 5-acetyl-1,3-di-acryloylhexahydro-1,3,5-triazine and other connections, which contain a reactive olefin bond (US-A-3 635,718, U.S.-A-3,232,763 and GB-A-994,869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732,316 and US-A-2,586,168); Isocyanates (U.S.-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbamoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (U.S.-A-4 111,926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308), compounds with two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), Isoxazole type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate,

The hardening can be effected in a known manner by that the hardening agent of the casting solution for the hardening layer is added, or in that the Layer to be hardened is covered with a layer which contains a diffusible hardening agent.

Among the classes listed there are slow-acting ones and fast-acting hardeners and so-called Instant hardeners that are particularly beneficial. Under Immediate hardeners are understood as connections that are suitable Crosslink the binder so that immediately after Watering, at the latest after 24 hours, preferably Hardening is completed after 8 hours at the latest is that no more through the crosslinking reaction conditional change in sensitometry and Swelling of the layer structure occurs. Under swelling is the difference between the wet film thickness and dry film thickness in the aqueous processing of the film understood (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Closely. (1972), 449).

These hardening agents that react very quickly with gelatin is it e.g. carbamoylpyridinium salts, those with free carboxyl groups of gelatin able to react, so that the latter with free amino groups gelatin to form peptide bonds and crosslinking of the gelatin react.

(a)

worin

R¹

Alkyl, Aryl oder Aralkyl bedeutet,

R²

die gleiche Bedeutung wie R¹ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel

verknüpft ist, oder

R¹ und R²

zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen
Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

R³

für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR⁴-COR⁵, -(CH₂)_m-NR⁸R⁹, -(CH₂)_n-CONR¹³R¹⁴ oder

oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei

R⁴, R⁶, R⁷, R⁹, R¹⁴, R¹⁵, R¹⁷, R¹⁸, und R¹⁹

Wasserstoff oder C₁-C₄-Alkyl,

R⁵

Wasserstoff, C₁-C₄-Alkyl oder NR⁶R⁷,

R⁸

-COR¹⁰

R¹⁰

NR¹¹R¹²

R¹¹

C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

R¹²

Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

R¹³

Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

R¹⁶

Wasserstoff, C₁-C₄-Alkyl, -COR¹⁸ oder -CONHR¹⁹,

m

eine Zahl 1 bis 3

n

eine Zahl 0 bis 3

p

eine Zahl 2 bis 3 und

Y

O oder NR¹⁷ bedeuten oder

R¹³ und R¹⁴

gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

Z

die zur Vervollständigung eines 5- oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und

X^⊖

ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;

(b)

worin

R¹, R², R³ und X^⊖

die für Formel (a) angegebene Bedeutung besitzen.

Suitable examples of instant hardeners are, for example, compounds of the general formulas

(a)

wherein

R ¹

Means alkyl, aryl or aralkyl,

R ²

has the same meaning as R ¹ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula

is linked, or

R ¹ and R ²

together those to complete an optionally substituted heterocyclic
A ring, for example a piperidine, piperazine or morpholine ring, are required atoms, it being possible for the ring to be substituted, for example, by C ₁ -C ₃ alkyl or halogen,

R ³

for hydrogen, alkyl, aryl, alkoxy, -NR ⁴ -COR ⁵ , - (CH ₂ ) _m -NR ⁸ R ⁹ , - (CH ₂ ) _n -CONR ¹³ R ¹⁴ or

or a bridge link or a direct bond to a polymer chain, wherein

R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , and R ¹⁹

Hydrogen or C ₁ -C ₄ alkyl,

R ⁵

Hydrogen, C ₁ -C ₄ alkyl or NR ⁶ R ⁷ ,

R ⁸

-COR ¹⁰

R ¹⁰

NR ¹¹ R ¹²

R ¹¹

C ₁ -C ₄ alkyl or aryl, especially phenyl,

R ¹²

Hydrogen, C ₁ -C ₄ alkyl or aryl, especially phenyl,

R ¹³

Hydrogen, C ₁ -C ₄ alkyl or aryl, especially phenyl,

R ¹⁶

Hydrogen, C ₁ -C ₄ alkyl, -COR ¹⁸ or -CONHR ¹⁹ ,

m

a number 1 to 3

n

a number 0 to 3

p

a number 2 to 3 and

Y

O or NR ¹⁷ mean or

R ¹³ and R ¹⁴

together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, for example, by C ₁ -C ₃ alkyl or halogen,

Z.

the carbon atoms required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring, and

X ^⊖

mean an anion which is omitted if an anionic group is already linked to the rest of the molecule;

(b)

wherein

R ¹ , R ² , R ³ and X ^⊖

have the meaning given for formula (a).

There are diffusible hardeners that work on everyone Layers within a layer group in the same Wise hardening. But there are also shift-limited ones acting, non-diffusing, low molecular weight and high molecular hardener, with them you can single Layers, e.g. crosslink the protective layer particularly strongly. This is important when looking at the silver halide layer little hardens due to the increase in silver opacity and with the protective layer the mechanical properties must improve (EP-A-0 114 699).

Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine, N-ethyl-N-3-hydroxypropyl-3-methyl-p-phenylenediamine and 1- (N- Ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

After color development, an acidic stop bath or follow a watering.

Usually the material is immediately after the Color development bleached and fixed. As a bleach can e.g. Fe (III) salts and Fe (III) complex salts such as Ferricyanides, dichromates, water-soluble cobalt complexes be used. Iron (III) complexes are particularly preferred of aminopolycarboxylic acids, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, nitrilotriacetic acid, Iminodiacetic acid, N-hydroxyethylethylenediamine triacetic acid, Alkyliminodicarboxylic acids and of corresponding phosphonic acids. Suitable as Bleaching agents are persulfates and peroxides, e.g. Hydrogen peroxide.

The bleach-fixing bath or fixing bath is usually followed by one Irrigation, which is carried out as countercurrent irrigation or consists of several tanks with their own water supply.

Favorable results can be obtained by using one on it following final bath, which little or no Contains formaldehyde can be obtained.

However, the watering can be completed by a stabilizing bath to be replaced, usually in countercurrent to be led. This stabilizing bath takes over when formaldehyde is added also the function of a final bath.

In the case of color reversal materials, development initially takes place with a black and white developer whose oxidation product not able to react with the color couplers is. A diffuse second exposure closes and then developing with a color developer, Bleach and fix.

example 1

Color photographic recording materials were like follows manufactured

a) Production of the color coupler emulgate

8 mmol color coupler are in the same weight Dibutyl phthalate (DBP) and three times the amount by weight Ethyl acetate in the presence of 0.15 g of dioctyl sulfosuccinate dissolved at a temperature of 50 to 70 ° C. The solution may also be used 25% by weight, based on the amount of couplers to be tested added light stabilizing compound. The solution is then in 150 g of 7.5 wt .-% aqueous, about 40 ° C warm gelatin solution stirred in and dispersed therein. Ethyl acetate is distilled off.

Dibutyl phthalate is optionally replaced by the same Amount of polymer oil former replaced.

b) Production of the color photographic to be tested Recording materials

The emulsifier produced under a) is mixed with a silver halide emulsion mixed that 8.2 g of silver in shape of silver halide, 9.2 g gelatin and 0.04 g sodium dodecylbenzenesulfonate contains. The total volume is adjusted to 350 ml with water. The so made Pouring solution is on a layer of cellulose triacetate shed.

c) processing and evaluation

After drying, the material is behind a step wedge exposed and color developed as usual, being as Color developer substance 2-amino-5- (N-ethyl-N-methanesulfonamidoethylamino) toluene was used.

0,07 g Dioctylhydrochinon und 0,36 g Trikresylphosphat aufgetragen. Die Mengen beziehen sich auf 1 m². Dichteabnahme in % bei Nr. Kuppler Verbindung I Ölformer D = 0,5 D = 1,0 D_max 1 Vergleich Y-9 - DBP 31 37 50 2 erfindungsgemäß Y-9 I-4 DBP 15 11 18 3 erfindungsgemäß Y-9 I-4 P 8 9 6 9 4 erfindungsgemäß Y-9 I-4 P 1 12 9 15 5 Vergleich Y-9 V-1 DBP 17 12 20 Dichteabnahme in % bei Nr. Kuppler Verbindung I (Zusatz 20 %) Ölformer D = 0,5 D = 1,0 D_max 1 Vergleich Y-12 - DBP 35 32 40 2 erfindungsgemäß Y-12 I-4 DBP 19 14 20 3 erfindungsgemäß Y-12 I-4 P 8 8 8 11 4 erfindungsgemäß Y-12 I-4 P 1 10 12 15 The processed samples are then covered with a UV protective film and irradiated in a Xenotest device to determine the light fastness (40% relative humidity; 25 ° C; 9.6 · 10 ⁶ 1x · h). The UV protective film was made as follows. A layer of 1.5 g of gelatin, 0.65 g of compound A (UV absorber) of the following formula was placed on a transparent cellulose triacetate film provided with an adhesive layer

0.07 g dioctyl hydroquinone and 0.36 g tricresyl phosphate applied. The amounts relate to 1 m ² . Density decrease in% No. Coupler Compound I Oil former D = 0.5 D = 1.0 D _max 1 comparison Y-9 - DBP 31 37 50 2 according to the invention Y-9 I-4 DBP 15 11 18th 3 according to the invention Y-9 I-4 P 8 9 6 9 4 according to the invention Y-9 I-4 P 1 12th 9 15 5 comparison Y-9 V-1 DBP 17th 12th 20th Density decrease in% No. Coupler Compound I (additional 20%) Oil former D = 0.5 D = 1.0 D _max 1 comparison Y-12 - DBP 35 32 40 2 according to the invention Y-12 I-4 DBP 19th 14 20th 3 according to the invention Y-12 I-4 P 8 8th 8th 11 4 according to the invention Y-12 I-4 P 1 10th 12th 15

Die Versuche zeigen, daß die Verbindungen der Formel (I) zwar eine stabilisierende Wirkung aufweisen, wenn Dibutylphthalat als Ölformer verwendet wird, gegenüber solchen Versuchen, in denen kein Stabilisator eingesetzt wird, daß diese Wirkung aber nicht merklich besser ist als die Wirkung der Vergleichssubstanz V-1. Hingegen wird bei der gemeinsamen Verwendung der Verbindungen der Formel (I) und der polymeren Ölformer eine erhebliche Verbesserung der stabilisierenden Wirkung gefunden. The compound V-1 (comparative stabilizer) has the formula

The experiments show that the compounds of the formula (I) have a stabilizing effect when dibutyl phthalate is used as an oil former, compared to experiments in which no stabilizer is used, but that this effect is not markedly better than the effect of the comparative substance V -1. In contrast, when the compounds of the formula (I) and the polymeric oil formers are used together, a considerable improvement in the stabilizing effect is found.

Example 2

A color photographic recording material was produced by applying the following layers in the order given on a paper coated on both sides with polyethylene. The quantities given relate to 1 m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application.

Layer structure 1

1. Schicht (Substratschicht)
   0,2 g Gelatine

2. Schicht (blauempfindliche Schicht)
   blauempfindliche Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,78 µm) aus 0,50 g AgNO₃ mit

1,38 g Gelatine

0,60 g Gelbkuppler Y-1

0,48 g Trikresylphosphat (TKP)

0,18 g Stabilisator gemäß Tabelle 3

3. Schicht (Zwischenschicht)

1,18 g Gelatine

0,08 g 2,5-Dioctylhydrochinon

0,08 g Dibutylphthalat (DBP)

4. Schicht (grünempfindliche Schicht)
   grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,37 µm) aus 0,40 g AgNO₃ mit

1,02 g Gelatine

0,37 g Purpurkuppler M-1

0,40 g DBP

5. Schicht (Zwischenschicht)

1,20 g Gelatine

0,66 g UV-Absorber der Formel

0,052 g 2,5-Dioctylhydrochinon

0,36 g TKP

6. Schicht (rotempfindliche Schicht)
   rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,35 µm) aus 0,28 g AgNO₃ mit

0,84 g Gelatine

0,39 g Blaugrünkuppler C-1

0,39 g TKP

7. Schicht (UV-Schutzschicht)

0,65 g Gelatine

0,21 g UV-Absorber wie in 5. Schicht

0,11 g TKP

8. Schicht (Schutzschicht)

0,65 g Gelatine

0,39 g Härtungsmittel der Formel

Proben der Schichtaufbauten wurden anschließend hinter einem graduierten Graukeil belichtet. Danach wurden die Materialien mit den nachfolgend aufgeführten Verarbeitungsbädern in der üblichen Weise verarbeitet.

1st layer (substrate layer)
0.2 g gelatin

2nd layer (blue-sensitive layer)
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.78 µm) from 0.50 g AgNO ₃ with

1.38 g gelatin

0.60 g yellow coupler Y-1

0.48 g tricresyl phosphate (CPM)

0.18 g stabilizer according to Table 3

3rd layer (intermediate layer)

1.18 g gelatin

0.08 g 2,5-dioctyl hydroquinone

0.08 g dibutyl phthalate (DBP)

4th layer (green-sensitive layer)
green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.37 µm) from 0.40 g AgNO ₃ with

1.02 g gelatin

0.37 g purple coupler M-1

0.40 g DBP

5th layer (intermediate layer)

1.20 g gelatin

0.66 g UV absorber of the formula

0.052 g 2,5-dioctyl hydroquinone

0.36 g CPM

6th layer (red-sensitive layer)
red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.35 µm) from 0.28 g AgNO ₃ with

0.84 g gelatin

0.39 g of cyan coupler C-1

0.39 g CPM

7th layer (UV protective layer)

0.65 g gelatin

0.21 g UV absorber as in 5th layer

0.11 g CPM

8th layer (protective layer)

0.65 g gelatin

0.39 g of curing agent of the formula

Samples of the layered structures were then exposed behind a graduated gray wedge. The materials were then processed in the customary manner using the processing baths listed below.

a) Color developer - 45 s - 35 ° C

Triethanolamine 9.0 g / l NN-diethylhydroxylamine 4.0 g / l Diethylene glycol 0.05 g / l 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl aniline sulfate 5.0 g / l Potassium sulfite 0.2 g / l Triethylene glycol 0.05 g / l Potassium carbonate 22 g / l Potassium hydroxide 0.4 g / l Ethylenediaminetetraacetic acid di-Na salt 2.2 g / l Potassium chloride 2.5 g / l 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.3 g / l make up to 1000 ml with water; pH 10.0

b) bleach-fix bath 45 s - 35 ° C

Ammonium thiosulfate 75 g / l Sodium bisulfite 13.5 g / l Ammonium acetate 2.0 g / l Ethylenediaminetetraacetic acid (iron ammonium salt) 57 g / l Ammonia 25% by weight 9.5 g / l acetic acid 9.0 g / l make up to 1000 ml with water; pH 5.5

c) Soak - 2 min - 35 ° C d) drying

The color images obtained were subjected to the Xenotest with 14.4 million Lxh at different yellow densities in accordance with ISO 10 977 (1/2 fog correction). The results are shown in Table 3. % Change in color density sample stabilizer Density 0.6 Density 1.0 Density 1.4 1 - - 40 - 31 - 27 2nd I-4 - 15th - 9 - 10th 3rd V-1 - 23 - 19th - 20th 4th V-2 - 20th - 10th - 11 5 V-3 - 16th - 12th - 11 6 V-4 - 21 - 14 - 13th 7 V-5 - 35 - 26 - 22 8th I-7 - 16th - 10th - 10th

Samples 2 and 8 are according to the invention.

The comparison stabilizers had the following formulas

Example 3

The following two layers were applied to a paper coated on both sides with polyethylene. The quantities relate to 1 m ² each.

1st layer

Blue-sensitive silver halide emulsion according to Example 2 from 0.6 g AgNO ₃ 2 g gelatin 0.8 g Yellow coupler Y-1 0.6 g CPM 0.24 g Stabilizer according to table 4

2nd layer (layer protection)

2 g gelatin 0.4 g Hardening agent according to Example 2 Processing takes place as in example 2.

The processed material was further stored in a climatic oven (80 ° C, 50% relative humidity, 21 days), the yellow dye decomposing into colored products according to the attached table. The densities behind the red and green filters before and after storage in a climatic chamber (for densities of 1.0 and 2.0 before storage behind a blue filter) were determined with a hand densitometer. The percent density increases are given in Table 4. Additional density in% at sample stabilizer Density 1.0 Density 2.0 and green filter and red filter and green filter and red filter 9 - + 31 + 24 + 37 + 19 10th I-4 + 5 + 10 + 20 + 10 11 V-1 + 25 + 12 + 46 + 14 12th V-2 + 28 + 13 + 42 + 15 13 V-3 + 28 + 17 + 45 + 13 14 V-4 + 26 + 17 + 42 + 15 15 V-6 + 25 + 16 + 33 + 15 16 I-7 + 7 + 12 + 22 + 12

Proben 10 und 16 sind erfindungsgemäß. Comparative stabilizer V-6 has the following formula

Samples 10 and 16 are according to the invention.

Example 4

Example 3 was repeated with the change that instead of the yellow coupler Y-1 the Yellow coupler Y-2 was used in the same amount.

After processing, the material was subjected to climatic cabinet storage (80 ° C., relative humidity, 21 days). The results are shown in Table 5. Additional density in% at sample stabilizer Density 1.0 Density 2.0 and green filter and red filter and green filter and red filter 17th - + 29 + 24 + 60 + 30 18th I-4 + 2 + 15 + 9 + 16 19th V-1 + 18 + 21 + 33 + 18 20th V-2 + 7 + 20 + 60 + 26 21 V-6 + 28 + 21 + 54 + 21 22 V-7 + 7 + 22 + 38 + 24 23 V-5 + 20 + 19 + 30 + 22 24th I-7 + 5 + 16 + 12 + 18

Proben 18 und 24 sind erfindungsgemäß.Comparative stabilizer V-7

Samples 18 and 24 are in accordance with the invention.

As Examples 3 and 4 show, the samples 10 and 16 and 18 and 24 the increase in the secondary densities due to storage in a climatic chamber less than the comparison samples. This keeps the natural color rendering preserved even after storage under unfavorable climatic conditions.

Claims (3)

1. Colour photographic material which contains on a support at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, together with conventional non-photosensitive layers, characterised in that at least one layer contains a compound of the formula (I)

   

   or an oligomeric or polymeric compound obtained by polymerisation of a compound of the formula (I), in which

   R₉

   identically or differently mean a residue

   

   R₁₀

   identically or differently mean an alkyl group, in particular having 1 to 9 C atoms,

   R₁₁

   means H or alkyl,

   R₁₂

   means H, aryl or alkyl,

   R₁₃

   means H, aryl or alkyl,

   R₁₄, R₁₅

   identically or differently mean an alkyl group, in particular having 1 to 4 C atoms,

   R₁₆

   means H or an alkyl group, in particular having 1 to 4 C atoms.

2. Colour photographic material according to claim 1, characterised in that the two residues R₉ are identical and the two residues R₁₀ are identical.
3. Colour photographic silver halide material according to claim 1, characterised in that the silver halide emulsions are at least 80 mol.% AgCl emulsions.