EP0586974A1 - Silver halide colour photographic material - Google Patents

Abstract

A photographic material comprising at least one silver halide emulsion layer which contains a colour coupler dispersed in a polymeric oil former and at least one compound of the formula (I) <IMAGE> where R is alkyl, cycloalkyl, alkenyl, aryl, acyl, alkylsulphonyl or arylsulphonyl, R1 is a chemical bond or a divalent bridge-type link, R2 and R3 are alkyl, alkoxy, alkenyl, cycloalkyl, aryl or aryloxy or two radicals R2 and R3 are the remaining atoms of a benzene ring condensed with the phenyl radical, and m and n are 0 to 3, it being possible for all the alkyl, alkoxy, cycloalkyl, alkenyl, aryl, aryloxy and acyl radicals to be additionally substituted, is notable for an improved colour stability.

Description

The invention relates to a color photographic silver halide material which has at least one yellow-coupling silver halide emulsion layer on a support and is characterized by improved light stability of the azomething yellow dye produced by the processing.

It is known to produce colored photographic images by chromogenic development, that is to say by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances with the color coupler which is formed in accordance with the silver image being formed of a dye image reacts. Aromatic compounds containing primary amino groups, especially those of the p-phenylenediamine type, are usually used as color developers.

It is also known that the image dyes produced by chromogenic development undergo certain changes to varying degrees under the influence of environmental conditions. The influence of light is of particular influence. As is known, the yellow azomethine dyes produced from the open-chain ketomethylene compounds bleach particularly strongly, while the cyan dyes produced from phenolic or naphtholic couplers prove to be quite stable and the magenta dyes produced from pyrazolone couplers have now been approximated in their light stability to the cyan couplers by adding suitable stabilizers.

The object of the invention was therefore to improve the light stability of the yellow dyes, so that the prolonged exposure to light on color photos with initially balanced colors does not cause uneven bleaching of the dyes, which would result in the appearance of a color cast. The agents proposed for improving the lightfastness of the purple dyes are only suitable to a limited extent for the stabilization of the yellow dyes and, moreover, often have other disadvantages which make them appear unsuitable for practical use. As hydroquinones or hydroquinone derivatives, they are easily oxidizable and often give rise to undesirable coloring (yellowing) of the image whites. When stored for a long time, they are often oxidized by the action of atmospheric oxygen or other oxidizing agents and thus lose their effectiveness.

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

From EP 246 766 bisphenol compounds are known in which a phenolic hydroxyl group is substituted. In terms of their light-stabilizing effect, these are no better than the free bisphenols of GB 1 267 287, but they lead to slightly purer colors.

It has now surprisingly been found that bisphenol derivatives with a substituted phenolic OH group, together with polymeric oil formers, considerably improve the light stability of the yellow azomethine dyes without any impairment of the color purity or a coloration of the image whites being found.

Polymeric oil formers are compounds which are soluble in organic solvents and have a unit which repeats at least twice in the molecule and whose boiling point is above 200 ° C., in which color couplers can be dissolved or dispersed.

worin

R

Alkyl, Cycloalkyl, Alkenyl, Aryl, Acyl, Alkylsulfonyl oder Arylsulfonyl,

R₁

eine chemische Bindung oder ein zweiwertiges Brückenglied,

R₂ und R₃

Alkyl, Alkoxy, Alkenyl, Cycloalkyl, Aryl oder Aryloxy oder zwei Reste R₂ bzw. R₃ die restlichen Atome eines mit dem Phenylrest kondensierten Benzolringes und

m und n

0 bis 3 bedeuten, wobei alle Alkyl-, Alkoxy-, Cycloalkyl-, Alkenyl-, Aryl-, Aryloxy- und Acylreste weitersubstituiert sein können,

enthält.The invention relates to a color photographic material with at least one silver halide emulsion layer, the at least one color coupler distributed in a polymeric oil former and at least one compound of the formula (I)

wherein

R

Alkyl, cycloalkyl, alkenyl, aryl, acyl, alkylsulfonyl or arylsulfonyl,

R₁

a chemical bond or a divalent bridge member,

R₂ and R₃

Alkyl, alkoxy, alkenyl, cycloalkyl, aryl or aryloxy or two radicals R₂ or R₃ the remaining atoms of a benzene ring condensed with the phenyl radical and

m and n

0 to 3, where all alkyl, alkoxy, cycloalkyl, alkenyl, aryl, aryloxy and acyl radicals can be further substituted,

contains.

Suitable bridge members R₁ are e.g. Alkylene, alkylidene or sulfonyl groups and heteroatoms such as O and S. Examples of R are methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, acetyl and benzyl.

worin

R₄, R₅, R₇ und R₈

Alkyl oder Aryl und

R₆

Wasserstoff oder Alkyl

bedeuten, wobei die Alkyl- und Arylreste substituiert sein können.Preferred compounds of the formula (I) are those of the general formula (II)

wherein

R₄, R₅, R₇ and R₈

Alkyl or aryl and

R₆

Hydrogen or alkyl

mean, where the alkyl and aryl radicals can be substituted.

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 furthermore relates to a color photographic recording material which comprises a compound of the formula (IV) in at least one layer.

contains what

R₉

the same or different a rest

R₁₀

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

R₁₁

H or alkyl,

R₁₂

H, aryl or alkyl,

R₁₃

H, aryl or alkyl,

R₁₄, R₁₅

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

R₁₆

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

With these compounds, improved stability of the yellow coupler is achieved even without a polymeric oil former.

Preferably, the two radicals R₉ are identical, as are the two radicals R₁₀. R₉ is preferably isopropyl, tert-butyl, cyclohexyl, tert-amyl and 1-methylcyclohexyl. R₁₀ is preferably methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, nonyl.

R₁₁, R₁₂, R₁₃ are in particular H or CH₃.

Verbindung R₂ R₂' R₃ R₄ I-6 C₂H₅ C₂H₅ H H I-7 t-C₄H₉ t-C₄H₉ H H I-8 n-C₄H₉ n-C₄H₉ H H I-9 CH₃ CH₃ H H I-10 C₉H₁₉ C₉H₁₉ H H I-11 C₂H₅ C₂H₅ CH₃ H I-12 CH₃ CH₃ CH₃ H I-13 CH₃ CH₃ H CH₃ I-14 CH₃ CH₃ H C₆H₅ I-15 t-C₄H₉ t-C₄H₉ CH₃ H
sowie

Verbindungen der Formeln (I), (II) und (IV), die polymerisierbare Doppelbindungen enthalten, z.B. I-5 bis I-18, können auch in oligomerer oder polymerer Form vorliegen.Suitable examples are the following compounds

connection R₂ R₂ ' R₃ R₄ I-6 C₂H₅ C₂H₅ H H I-7 t-C₄H₉ t-C₄H₉ H H I-8 n-C₄H₉ n-C₄H₉ H H I-9 CH₃ CH₃ H H I-10 C₉H₁₉ C₉H₁₉ H H I-11 C₂H₅ C₂H₅ CH₃ H I-12 CH₃ CH₃ CH₃ H I-13 CH₃ CH₃ H CH₃ I-14 CH₃ CH₃ H C₆H₅ I-15 t-C₄H₉ t-C₄H₉ CH₃ H
such as

Compounds of the formulas (I), (II) and (IV) which contain polymerizable double bonds, for example I-5 to I-18, can also be present in oligomeric or polymeric form.

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

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

Examples of 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, cyanoethylacrylate, 2-acetoxyethyl acrylate, dimethyl acrylate, cycloethyl acrylate, cycloethyl acrylate, methacrylate, 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-methacrylic amide); 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 the addition of a free radical which is formed by thermal decomposition of a chemical initiator by action of a reducing agent on an oxidizing compound (redox initiator) or by physical action, such as radiation 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 (e.g. 4,4'-azobis-4-cyanovaleric acid or azobisisobutyronitrile).

Examples of conventional redox initiators include hydrogen peroxide iron (II) salt, potassium persulfate, sodium metabisulfite and cerium IV salt alcohol, etc.

Examples of the initiators and their functions are described by F.A. Bovey, in emulsion polymerization, Interscience Publishers Inc., New York, 1955, pages 59-93.

A compound with a surface-active effect is used as the emulsifier which can be used in the emulsion polymerization. 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, especially 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. Polyester made by ring opening polycondensation

These polyesters are made from β-propiolactone, α-caprolactone and dimethylpropiolactone.

4. Other polymers

Polycarbonates made by polycondensing 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 polycondensing a polyhydric amine and a polybasic acid, phenol aldehyde resins made by polycondensing phenols and aldehyde; Alkylene oxide addition products of phenol aldehyde resins, polyaddition products of alkylene oxides; Polyepoxides obtained by reacting bisphenols, alcohols, diamines or sulfur-containing compounds (such as dithiophenols), phenol aldehyde resins, polyalcohols, polycarboxylic acids, polyamines with epihalohydrin (e.g. 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 polymeric oil formers correspond to the formula (III)

wherein

R₉ and R₁₀

Alkyl

R₁₁

Hydrogen or alkyl

X

-CH₂-CH₂- or

R₁₂

Alkyl

O

1 to 10

p

0 to 20

mean.

Preferably R₉ is hydrogen and R₁₀ is a C₁-C₁₂ alkyl radical, which is in particular p-to the oxygen.

R₁₁ is especially hydrogen; R₁₂ is especially methyl; o is in particular 1 to 5; p is in particular 0 to 5.

Die bevorzugten polymeren Ölformer werden durch Addition von Alkylenoxiden an Phenol-Aldehydharze hergestellt.Examples of preferred polymeric oil formers are polymers with the following structural units

The preferred polymeric oil formers are made by adding alkylene oxides to phenol aldehyde resins.

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

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

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 supports 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 paper laminated with a baryta layer or α-olefin polymer layer (e.g. polyethylene). These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.

It is preferably a color photographic paper with a paper laminated on both sides with polyethylene as a support.

The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.

Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.

Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.

The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used, the production Such gelatins are described, for example, in The Science and Technology of Gelatin, published by AG, Ward and A, Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.

The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used, in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are usually used up to pure silver chloride emulsions. These can be predominantly compact crystals which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is much greater than 5: 1, e.g. 12: 1 to 30: 1.

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

Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.

The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.

The silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being formed, should not be exceeded. The pAg range can vary within wide limits during precipitation, the so-called pAg-controlled method is preferably used , in which a certain pAg value is kept constant or a defined pAg profile is run through during the precipitation, in addition to the preferred precipitation in the case of excess halide, so-called inverse precipitation in the case of excess silver ions is also possible, in addition to precipitation, the silver halide crystals can also be physically ripened ( Ostwald ripening), grow in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and the like nd is redeemed on the latter.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.

The precipitation can also be carried out in the presence of sensitizing dyes. Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.

The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached. The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).

The chemical sensitization with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII Periodic table (e.g. gold, platinum, palladium, iridium), thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described for example by F. Hamer "The Cyanine Dyes and Related Compounds") , 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 18, pp. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III). As an alternative or in addition, a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.

Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles can also be used as antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts. 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 be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Mixtures of two or more of the compounds mentioned can also be used.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics ( eg acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. saponin, mainly synthetic surface-active compounds (surfactants) are used: non-ionic surfactants, e.g. alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, e.g. higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, containing anionic surfactants Acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.

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

Research Disclosure 17643 (Dec. 1978), Chapter IV, provides an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations having a super-sensitizing effect.

• 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-ethyl carbocyanines with benzothiazole, 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 -selencarbocyanines and 9- Ethyl naphthothiaoxa or benzimidazocarbocyanines, 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 also benzimidazocarbocyanines, which may also be further substituted and must likewise 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 are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually, cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type. Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type. Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type, for example α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.

Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird Zu den 2-Äquivalentkupplern sind solche zu rechnen, die farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), und die Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR- bzw. FAR-Kuppler.Suitable yellow couplers include the following:

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include those that are colorless and those that have an intense inherent color, which disappears during the color coupling or is replaced by the color of the image dye produced (mask coupler), and the white couplers which, when reacted with color developer oxidation products, essentially give colorless products. The 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( 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 activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.

DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described 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. DIR couplers of this type provide further advantages for color reproduction, ie color separation and color purity, and for detail reproduction, ie sharpness and graininess to achieve, for example, the cleavage of the development inhibitor not directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved for example with a timing group. Examples of these 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 as well in GB-A-2 072 363.

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

When using DIR couplers, in particular those which release an easily diffusible development inhibitor, suitable measures can be taken to improve the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, 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 added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferred to the photosensitive silver halide emulsion layers added, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved. The influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it can be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.

To increase the sensitivity, the contrast and the maximum density, DAR or FAR couplers can be used, which release a development accelerator or an fogger. Compounds of this type are, 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 of the use of BAR couplers (Bleach Accelerator Releasing Coupler), reference is made to EP-A-193 389.

It can be advantageous to modify the effect of a photographically active group which is split off from a coupler in that an intermolecular reaction of this group occurs after its release with another group according to DE-A-35 06 805.

Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).

The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).

The material may further contain compounds other than couplers, which can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat 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. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.

High molecular weight color couplers are described, 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. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.

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

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.

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

The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to 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.-A-4,291,113.

The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.

Suitable oil formers are e.g. Alkyl phthalates, 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 dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 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, at least one silver halide emulsion layer contains a coupler distributed in a polymeric oil former in combination with a compound of the formula (I).

Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). In this case, red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

The non-light-sensitive ones, which are generally arranged between layers of different spectral sensitivity Intermediate layers can contain agents which prevent undesired diffusion of developer oxidation products from one photosensitive to another photosensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters 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, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sub-layer with higher sensitivity will be arranged further away from the support than the sub-layer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (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.

On the one hand, UV light-absorbing compounds are intended to protect the image dyes from fading due to UV-rich daylight and, on the other hand, as filter dyes, absorb UV light in daylight during exposure and thus improve the color rendering of a film. Usually, compounds of different structures are used for the two tasks . 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 α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.

Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are 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.

Certain binder layers, in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert 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 water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

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

Compounds which have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the deterioration of yellow color images as a result of the development of heat, moisture and light. In order to prevent the deterioration of magenta color images, in particular their deterioration as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are mono- or disubstituted by alkoxy groups (JP-A-89 835 / 80), particularly effective.

The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis- (2-chloroethylurea), 2-Hydroxy-4,6-dichloro-1,3,5-triazine and other 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-diacryloylhexahydro-1,3,5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-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 (US-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 (US-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 having 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 curing can be effected in a known manner in that the curing agent of the casting solution for the hardening layer is added, or by covering the layer to be hardened with a layer containing a diffusible hardening agent.

There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

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

• (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

  R¹

  Means alkyl, aryl or aralkyl,

  R²

  has the same meaning as R¹ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond being with a group of the formula

  

  is linked, or

  R1 and R2

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C₁-C₃alkyl or halogen,

  R³

  for hydrogen, alkyl, aryl, alkoxy, -NR⁴-COR⁵, - (CH₂) _m -NR⁸R⁹, - (CH₂) _n -CONR¹³R¹⁴ or

  

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

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

  Hydrogen or C₁-C₄ alkyl,

  R⁵

  Hydrogen, C₁-C₄-alkyl or NR⁶R⁷,

  R⁸

  -COR¹⁰

  R¹⁰

  NR¹¹R¹²

  R¹¹

  C₁-C₄ alkyl or aryl, especially phenyl,

  R¹²

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R¹³

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R¹⁶

  Hydrogen, C₁-C₄-alkyl, -COR¹⁸ or - CONHR¹⁹,

  m

  a number 1 to 3

  n

  a number 0 to 3

  p

  a number 2 to 3 and

  Y

  O or NR¹⁷ mean or

  R¹³ and R¹⁴

  together those to complete an optionally substituted heterocyclic ring, for example one Piperidine, piperazine or morpholine ring are required atoms, which ring can be substituted, for example by C₁-C₃-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

  R¹, R², R³ and X ^⊖

  have the meaning given for formula (a).

There are diffusible curing agents that have the same curing effect on all layers within a layer structure. However, there are also layer-limited, non-diffusing, low-molecular and high-molecular hardeners Crosslink layers, eg the protective layer particularly strongly. This is important if the silver halide layer is hardened little because of the increase in silver opacity and the mechanical layer has to be improved with the protective layer (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 the color development, an acidic stop bath or watering can follow.

Usually, the material is bleached and fixed immediately after color development. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used. Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulfates and peroxides, e.g. Hydrogen peroxide.

The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.

Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.

However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also acts as a final bath.

In the case of color reversal materials, development is first carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.

example 1

Color photographic materials were prepared as follows

a) Production of the color coupler emulgate

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

Dibutyl phthalate is optionally replaced by the same amount of polymeric oil former.

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

The emulsifier produced under a) is mixed with a silver halide emulsion which contains 8.2 g of silver in the form of silver halide, 9.2 g of gelatin and 0.04 g of sodium dodecylbenzenesulfonate. The total volume is adjusted to 350 ml with water. The casting solution thus produced is poured onto a layer of cellulose triacetate.

c) processing and evaluation

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

0,07 g Dioctylhydrochinon und 0,36 g Trikresylphosphat aufgetragen. Die Mengen beziehen sich auf 1 m².

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 · 10⁶ 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 quantities refer to 1 m².

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 those 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 to a paper coated on both sides with polyethylene. The amounts given relate in each case to 1 m 2. For the silver halide application, the corresponding amounts of AgNO₃ are given.

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 AgNO₃ 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 AgNO₃ 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 AgNO₃ 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. Table 3 sample stabilizer % Change in color density Density 0.6 Density 1.0 Density 1.4 1 - - 40 - 31 - 27 2nd I-9 - 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-12 - 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 refer to 1 m² each.

1st layer

Blue-sensitive silver halide emulsion according to Example 2 from 0.6 g AgNO₃
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 of curing 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. Table 4 sample stabilizer Additional density in% at 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-9 + 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-12 + 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 the yellow coupler Y-2 was used in the same amount instead of the yellow coupler Y-1.

Vergleichsstabilisator V-7

Proben 18 und 24 sind erfindungsgemäß.After processing, the material was subjected to climatic cabinet storage (80 ° C, 50% relative humidity, 21 days). The results are shown in Table 5. Table 5 sample stabilizer Additional density in% at 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-9 + 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-12 + 5 + 16 + 12 + 18

Comparative stabilizer V-7

Samples 18 and 24 are in accordance with the invention.

As Examples 3 and 4 show, in the samples 10 and 16 or 18 and 24 according to the invention, the increase in the secondary densities due to storage in a climatic oven is considerably less than in the comparative samples. As a result, the natural color rendering is retained even after storage under unfavorable climatic conditions.

Claims (9)

Color photographic material with at least one silver halide emulsion layer, a color coupler distributed in an oil former and at least one bisphenol compound of the formula (I)

wherein R alkyl, cycloalkyl, alkenyl, aryl, acyl, alkylsulfonyl or arylsulfonyl, R₁ is a chemical bond or a divalent bridge member, R₂ and R₃ alkyl, alkoxy, alkenyl, cycloalkyl, aryl or aryloxy or two radicals R₂ or R₃ the remaining atoms of a benzene ring condensed with the phenyl radical and m and n represent 0 to 3, where all alkyl, alkoxy, cycloalkyl, alkenyl, aryl, aryloxy and acyl radicals can be further substituted, contains, characterized in that the oil former is a polymeric oil former. Color photographic material according to claim 1, characterized in that the polymeric oil former of the formula (III)

corresponds to what R₉ and R₁₀ alkyl R₁₁ is hydrogen or alkyl X -CH₂-CH₂- or

R₁₂ alkyl o 1 to 10 p 0 to 20 mean corresponds. Color photographic material according to claim 1, characterized in that the bisphenol compound of formula (II)

corresponds to what R₄, R₅, R₇ and R₈ are alkyl or aryl and R₆ are hydrogen or alkyl and the alkyl and aryl radicals can be substituted. Color photographic material according to claim 1, characterized in that the bisphenol compound is used in an amount of 0.1 to 2 g / g of color coupler and the polymeric oil forms in an amount of 0.1 to 4 g / g of color coupler. Color photographic material according to claim 1, characterized in that the average molecular weight (weight average) of the polymeric oil former is not greater than 200,000. Color photographic material according to claim 1, characterized in that the color coupler distributed in the polymer oil forms is a yellow coupler. Color 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 and customary non-light-sensitive layers, characterized in that at least one Layer a compound of formula (IV)

contains what R₉ the same or different a remainder

R₁₀, the same or different, is an alkyl group, in particular with 1 to 9 carbon atoms, R₁₁ H or alkyl R₁₂ H, alkyl or aryl R₁₃ H, alkyl or aryl R₁₄ and R₁₅, the same or different, are an alkyl group, in particular with 1 to 4 carbon atoms and R₁₆ H or an alkyl group, in particular with 1 to 4 carbon atoms Color photographic material according to claim 7, characterized in that the two radicals R₉ are identical and the two radicals R₁₀ are identical. Color photographic silver halide material according to claims 1 and 7, characterized in that the silver halide emulsions are at least 80 mol% AgCl emulsions.