EP0631184B1 - Colour photographic recording material - Google Patents

Description

The invention relates to a color photographic recording material with improved dye stability.

Color photographic materials typically contain at least one yellow coupler, at least one purple coupler and at least one cyan coupler, from which through exposure and development the appropriate Dyes are created. These dyes, especially the Dyes that are constantly exposed to light should have high color stability, whereby special emphasis is placed on the color stability of all three colors is as good as possible, so there is no color falsification with a slight fading entry.

Especially yellow dyes that come from couplers an open chain ketomethylene grouping both need to be stabilized against light as well as against fading in the dark (dark fading).

In US-A-3 700 455 the proposal is already made this task with bisphenol compounds as stabilizers to solve. The effect achieved is, however not yet sufficient.

It has now surprisingly been found that certain Bisphenols can do this much better.

enthält, worin

X

-NH-, -NR- oder -O-,

R

Alkyl, Cycloalkyl oder Aryl,

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- und Aryloxyreste weitersubstituiert sein können und in jedem der beiden Phenylreste ein Rest R₁, R₂ oder R₃ para-ständig zum Sauerstoffatom ist.

The invention therefore relates to a 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 conventional non-light-sensitive layers. characterized in that at least one layer comprises a compound of formula (I)

contains what

X

-NH-, -NR- or -O-,

R

Alkyl, cycloalkyl or aryl,

R ₁

a chemical bond or a divalent bridge member,

R ₂ and R ₃

Alkyl, alkoxy, alkenyl, cycloalkyl, aryl or aryloxy, or two radicals R ₂ or R _3, the remaining atoms of a benzene ring condensed with the phenyl radical and

m and n

0 to 3 mean, where all alkyl, alkoxy, cycloalkyl, alkenyl, aryl and aryloxy radicals can be further substituted and in each of the two phenyl radicals a radical R ₁ , R ₂ or R _{3 is} para to the oxygen atom.

Suitable bridge members R ₁ are, for example, alkylene, alkylidene or sulfonyl groups and heteroatoms such as 0 and S. Examples of R are methyl, ethyl, propyl, tert-butyl, n-butyl, cyclohexyl, dodecyl, hexadecyl and benzyl.

worin

X

-NH, -O- oder -NR-

R₄, R₅, R₇ und R₈

Alkyl oder Aryl,

R₆

Alkyl, Cyclohexyl, Acryloxyethyl oder Methacryloxyethyl bedeuten.

R und R₁ die vorstehend angegebene Bedeutung haben und die Alkyl- und Arylreste weitersubstituiert sein können.Preferred compounds of the formula (I) are those of the formula (II)

wherein

X

-NH, -O- or -NR-

R ₄ , R ₅ , R ₇ and R ₈

Alkyl or aryl,

R ₆

Alkyl, cyclohexyl, acryloxyethyl or methacryloxyethyl mean.

R and R _{1 have} the meaning given above and the alkyl and aryl radicals can be further substituted.

Suitable compounds of formula I are:

The connections are preferably made in a color coupler Layer in an amount of 0.1 to 2 mol / mol color coupler, especially in an amount of 0.1 to 0.5 mol / mol color coupler used.

mit

Y =

ein unter den Bedingungen der chromogen Entwicklung abspaltbarer Rest, z.B. Acyl,

R³¹ =

Alkyl, Cycloalkyl, Acylamino, Sulfonamino,

R³², R³³, R³⁴ =

H, Alkyl, Cycloalkyl, Hydroxy, Acyloxy, Alkoxycarbonyl, Halogen, Acylamino, Carbamoyl,

R³⁵ =

Alkyl, Cycloalkyl, Alkoxycarbonyl, Acylamino, Carbamoyl.

In a preferred embodiment, the compounds of the formulas I and II are used in combination with other dye stabilizers, further dye stabilizers being compounds of the following formulas III, IV and V, which are preferably present in a color coupler-containing layer in an amount of 0.05 up to 2 mol / mol color coupler, in particular 0.05 to 0.5 mol / mol color coupler can be used.

With

Y =

a residue which can be split off under the conditions of chromogenic development, for example acyl,

R ³¹ =

Alkyl, cycloalkyl, acylamino, sulfonamino,

R ³² , R ³³ , R ³⁴ =

H, alkyl, cycloalkyl, hydroxy, acyloxy, alkoxycarbonyl, halogen, acylamino, carbamoyl,

R ³⁵ =

Alkyl, cycloalkyl, alkoxycarbonyl, acylamino, carbamoyl.

mit

R⁴¹ =

H, OH, Alkoxy, Aryloxy, Acyl, Acyloxy, Alkyl, Cycloalkyl,

R⁴², R⁴³ =

H, Alkyl,

R⁴⁴, R⁴⁵ =

Alkyl, Cycloalkyl,

Z =

Gruppe zu Vervollständigung eines nichtmetallischen 5- bis 8-Ringes.

Two adjacent radicals R ³¹ to R ³⁵ can form a 5- or 6-membered ring.

With

R ⁴¹ =

H, OH, alkoxy, aryloxy, acyl, acyloxy, alkyl, cycloalkyl,

R ⁴² , R ⁴³ =

H, alkyl,

R ⁴⁴ , R ⁴⁵ =

Alkyl, cycloalkyl,

Z =

Group for completing a non-metallic 5- to 8-ring.

R⁵¹, R⁵² =

Alkyl, Cycloalkyl, Aryl.

The radicals R ⁴² and R ⁴⁵ , R ⁴³ and R ⁴⁴ , R ⁴¹ and R ⁴⁴ or R ⁴⁵ can form a 5- to 8-membered ring. V R ⁵¹ -SR ⁵² With

R ⁵¹ , R ⁵² =

Alkyl, cycloalkyl, aryl.

The radicals R ⁵¹ and R ⁵² can also form a 5- to 8-membered ring.

The alkyl or aryl radicals can be substituted, for example by hydroxy, alkyl, aryl, hetaryl, alkoxy, Aryloxy, acyloxy, alkoxycarbonyl, acylamino, carbamoyl, Sulfonamino, sulfamoyl, sulfonyl and halogen.

An acyl residue can consist of a carboxylic acid (e.g. acetyl, Acrylic), a carbamic acid (e.g. dodecylaminocarbonyl, Butylaminocarbonyl) or a carbonic acid semi-ester (e.g. ethoxycarbonyl, hexyldecyloxycarbonyl).

The compounds III, IV and V can also have a of the substituents are bound to a polymer chain.

Examples of compounds of the formulas III, IV and V are

The compounds essential 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. Yellow couplers are preferably used in an amount of 0.1 to 1 mmol / m ² material.

Synthesis of compound I-4:

6.8 g of 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol) in 30 ml of acetone are stirred overnight at room temperature with 4.42 g of dodecyl isocyanate. The solution is poured into H ₂ O, the precipitate is filtered off, washed with water and dried at 40 ° C. in vacuo. For further purification, the mixture is stirred with methanol.
Yield: 55% mp: 112-116 ° C.

Synthesis of compound I-6:

6.8 g of 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol) in 30 ml of acetone are stirred overnight at room temperature with 3.1 g of isocyanatoethyl methacrylate. The solution is poured into H ₂ O, the residue is stirred with H ₂ O and dried in vacuo at 40 ° C. The solid is recrystallized from hexane.
Yield: 69% mp: 138-142 ° C

Synthesis of compound I-21

2.17 g of ethyl chloroformate are added dropwise at 0 ° C. to 6.8 g of 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol) and 2.02 g of triethylamine in 10 ml of acetone. The reaction solution is stirred for 4 hours at room temperature and then stirred with H ₂ O. The residue is filtered off and recrystallized from ethanol.
Yield: 85% mp: 129-130 ° C

In the yellow couplers, which are preferred with those essential to the invention Dye stabilizers used in one layer are preferably 2-equivalent pivaloyl yellow couplers, their leaving group either over oxygen or over nitrogen with the coupling position of the coupler is connected.

Suitable yellow couplers are:

The Träaer can be reflective or transparent.

As silver halo aides of color coupler and color coupler-free silver halide emulsion layers AgBr, AgBrCl, AgBrClI and AgCl come into consideration.

The silver halides preferably contain all photosensitive Layers including those essential to the invention Interlayer at least 80 mole percent chloride. in particular 95 to 100 mol% of chloride. 0 to 5 mol% Bromide and 0 to 1 mol% iodide. The silver halide emulsions can work directly positive or preferably be negative working emulsions.

The silver halide can be predominantly compact Act crystals that e.g. reactive cubic or are octahedral or may have overaana shapes. However, twins, e.g. platelet-shaped crystals are present, their average Ratio of diameter to thickness preferred less than 5: 1, the diameter being one Grain is defined as the diameter of a circle with a circle content corresponding to the projected Area of the grain. The layers can also be tabular Have silver halide crystals in which the ratio of diameter to thickness greater than 5: 1 is, 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. The emulsions can in addition to the silver halide, organic silver salts included, e.g. Silver benzotriazolate or silver behenate.

Two or more types of silver halide emulsions, which are manufactured separately as Mixture can be used.

The photographic emulsions can be different Methods (e.g. P. Glafkides. Chimie et Pysique Photographique, Paul Montel, Paris (1967), G.F. Duffin.

Photographic emulsion chemistry. The Focal Press. London (1966). V.L. Zelikman et al. Making and Coatina Photographic Emulsion. The Focal Press, London (1966)) soluble silver salts and soluble halides become.

The preferred binder for the silver halides is Gelatin used. However, this can be done entirely or partly by other synthetic, semi-synthetic or replacing naturally occurring polymers become.

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 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 from Birr, for example. 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 such as nitrobenzimidazole can also be used as antifoggants. Nitroindazole. (Subst.) Benztriazole or Benzthiazoliumsalze be used. 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 in Research Disclosure No. 17643 (1978). Section VI. released.

The stabilizers can the silver halide emulsions before, during or after their ripening. Of course you can also do the connections other photographic layers, that of a silver halide layer are assigned.

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

The silver halide emulsions are commonly used chemically matured, for example by exposure to Gold compounds or compounds of the divalent Sulfur.

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.).

1. Rotsensibilisatoren Dicarbocyanine mit Naphthothiazol oder Benzthiazol als basischen Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy substituiert sein können sowie 9.11-alkylen-verbrückte, insbesondere 9.11-Neopentylenthiadicarbocyanine mit Alkyl- oder Sulfoalkylsubstituenten am Stickstoff.

2. Grünsensibilisatoren 9-Ethyloxacarbocyanine, die in 5-Stellung durch Chlor oder Phenyl substituiert sind und am Stickstoff der Benzoxazolgruppen Alkyl- oder Sulfoalkylreste, vorzugsweise Sulfoalkylsubstituenten tragen.

3. Blausensibilisatoren Methincyanine mit Benzoxazol, Benzthiazol, Benzselenazol, Naphthoxazol, Naphthothiazol als basischen Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy substituiert sein können und mindestens eine, vorzugsweise zwei, Sulfoalkylsubstituenten am Stickstoff tragen, Ferner Apomerocyanine mit einer Rhodaningruppe.

Suitable sensitizing dyes are cyanine dyes, in particular of the following classes:

1. Red sensitizers dicarbocyanines with naphthothiazole or benzthiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy and 9.11-alkylene-bridged, in particular 9.11-neopentylenthiadicarbocyanines with alkyl or sulfoalkyl substituents on nitrogen.

2. Green sensitizers 9-ethyloxacarbocyanines which are substituted in the 5-position by chlorine or phenyl and carry alkyl or sulfoalkyl radicals, preferably sulfoalkyl substituents, on the nitrogen of the benzoxazole groups.

3. Blue sensitizers methine cyanine with benzoxazole, benzthiazole, benzselenazole, naphthoxazole, naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy and carry at least one, preferably two, sulfoalkyl substituents on nitrogen, furthermore Apomerocyanines with a rhodanine group.

Sensitizers can be dispensed with if for intrinsic sensitivity in a certain spectral range of the silver halide is sufficient, for example the blue sensitivity of silver bromide iodides.

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 generating the purple partial color image are usually pyrazolazole type couplers, 5-pyrazolone or indazolone.

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; suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers. As already mentioned, the latter are preferred.

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.

The couplers usually contain a ballast residue, diffusion within the material, i.e. either within a shift or from shift to shift, impossible to make. Instead of couplers with one Ballast residues can also be used with high molecular weight couplers become.

Suitable color couplers or references in which such are described in Research Disclosure 17 643 (1978), Chapter VII.

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 by polyaddition or polycondensation be preserved.

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 Insoluble compounds by grinding processes are for example described in DE-A-26 09 741 and DE-A-26 09 742.

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-0 043 037.

Instead of the high-boiling solvents, oligomers can 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, Hydrocarbons, sulfones and sulfoxides.

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-tert-amylphenol, Dioctyl acetate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5-tert-octylaniline, Paraffin, dodecylbenzene and diisopropylnaphthalene.

The photographic material can also contain UV light absorbing compounds, white toners, 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. In addition, intermediate layers can contain so-called white couplers and other compounds that react with the developer oxidant product (scavenger).

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-diacryloylhexahydro-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), compounds of isoxazole type (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 be that the curing agent of the casting solution for the layer to be hardened 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.

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).

The color photographic materials essential to the invention are usually processed by developing, bleaching, fixing and washing or 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, 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 after color development bleached and fixed. As bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, Dichromate, water-soluble cobalt complexes used become. Iron (III) complexes are particularly preferred of aminopolycarboxylic acids, especially e.g. from Ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, nitrilotriacetic acid, Iminodiacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, Alkyliminodicarboxylic acids and corresponding Phosphonic acids. Suitable as bleach 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 from several tanks with their own water supply consists.

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

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.

example 1

1. Schicht

Blauempfindliche Silberhalogenidemulsionsschicht aus 0,6 g AgNO₃

(99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,78 µm)

2 g Gelatine

0,8 g Gelbkuppler Y-9

0,6 g DBP

Stabilisator gemäß Tabelle 1 in einer Menge von 0,5 mol/mol Kuppler

2. Schicht

2 g Gelatine

0,4 g Härtungsmittel der Formel

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

1st layer

Blue-sensitive silver halide emulsion layer made of 0.6 g AgNO ₃

(99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.78 µm)

2 g gelatin

0.8 g yellow coupler Y-9

0.6 g DBP

Stabilizer according to Table 1 in an amount of 0.5 mol / mol coupler

2 layer

2 g gelatin

0.4 g hardening agent of the formula

a) Farbentwickler - 45 s - 35°C Triethanolamin 9,0 g/l NN-Diethylhydroxyamin 4,0 g/l Diethylenglykol 0,05 g/l 3-Methyl-4-amino-N-ethyl-N-methansulfonaminoethyl-anilin-sulfat 5,0 g/l Kaliumsulfit 0,2 g/l Triethylenglykol 0,05 g/l Kaliumcarbonat 22 g/l Kaliumhydroxid 0,4 g/l Ethylendiamintetraessigsäure-di-Na-Salz 2,2 g/l Kaliumchlorid 2,5 g/l 1,2-Dihydroxybenzol-3,4,6-trisulfonsäure-trinatriumsalz 0,3 g/l auffüllen mit Wasser auf 1000 ml; pH 10,0

b) Bleichfixierbad - 45 s - 35°C Ammoniumthiosulfat 75 g/l Natriumhydrogensulfit 13,5 g/l Arnoniumacetat 2,0 g/l Ethylendiamintetraessigsäure (Eisen-Ammonium-Salz) 57 g/l Ammoniak 25 gew.-%ig 9,5 g/l Essigsäure 9,0 g/l auffüllen mit Wasser auf 1000 ml; pH 5,5

c) Wässern - 2 min - 35°C

d) Trocknen

The samples were then exposed behind a graduated gray wedge and processed in the customary manner with the processing baths listed below.

a) Color developer - 45 s - 35 ° C Triethanolamine 9.0 g / l NN-diethylhydroxyamine 4.0 g / l Diethylene glycol 0.05 g / l 3-methyl-4-amino-N-ethyl-N-methanesulfonaminoethyl 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 Arnonium 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 processed samples are then covered with a UV protective film and irradiated in a xenon test device to determine the light fastness (40% relative humidity; 25 ° C; 19.2 ^. 10 ⁶ lxh).

0,07 g Dioctylhydrochinon und 0,36 g Trikresylphosphat aufgetragen. Die Mengen beziehen sich auf 1 m². Probe Stabilisator Dichteabnahme in % bei Dichte 0,5 1,0 D_max 1 Vergleich - 75 74 77 2 Vergleich X-1 63 57 53 3 Vergleich X-2 65 59 50 4 Vergleich X-3 62 56 49 5 Erfindung I-4 41 25 33 6 Erfindung I-6 44 26 37 7 Erfindung I-14 45 27 36 8 Erfindung I-21 46 27 37 9 Erfindung I-25 42 24 32 The UV protective film was produced as follows: A layer of 1.5 g of gelatin, 0.65 g of 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 . sample stabilizer Density decrease in% at density 0.5 1.0 D _max 1 comparison - 75 74 77 2nd comparison X-1 63 57 53 3rd comparison X-2 65 59 50 4th comparison X-3 62 56 49 5 invention I-4 41 25th 33 6 invention I-6 44 26 37 7 invention I-14 45 27 36 8th invention I-21 46 27 37 9 invention I-25 42 24th 32

As Table 1 shows, the compounds essential to the invention achieve improved light stability of the yellow dyes, especially at medium and high densities.

Example 2

A color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of 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 sample 1

Layer 1:

(Substrate layer)
0.2 g gelatin

Layer 2:

(blue sensitive layer)
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm)
0.45 g AgNO ₃ with
1.08 g gelatin
0.60 g yellow coupler Y-21
0.215 g white coupler W-1
0.30 g tricresyl phosphate (CPM)

Layer 3:

(Protective layer)
1.1 g gelatin
0.06 g 2,5-diotyl hydroquinone
0.06 g dibutyl phthalate (DBP)

Layer 4:

(green sensitive layer)
green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm)
from 0.45 g AgNO ₃ with
1.08 g gelatin
0.41 g purple coupler M-1
0.15 g ST-1 image stabilizer
0.30 g image stabilizer ST-2
0.08 g 2,5-dioctyl hydroquinone
0.34 g DBP
0.04 g CPM

Layer 5:

(UV protective layer)
1.15 g gelatin
0.6 g UV absorber UV-1
0.045 g 2,5-dioctyl hydroquinone
0.04 g CPM

Layer 6:

(red sensitive layer)
red-sensitized silver halide emulsion
(99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm)
0.3 g of AgNO ₃ with
0.75 g gelatin
0.36 g of cyan coupler C-1
0.36 g CPM

Layer 7:

(UV protective layer)
0.35 g gelatin
0.15 g UV absorber UV-1
0.2 g CPM

Layer 8:

(Protective layer)
0.9 g gelatin
0.3 g of H-1 curing agent

Samples 2 to 13

Samples 2 to 13 were produced in the same way as sample 1, with the difference that 0.2 g / m ^{2 of} a stabilizer shown in table 2 was added to layer 2.

Samples 9 to 13 additionally had 0.1 g / m ^{2 of} a costabilizer of the formulas III, IV or V given in table 2 added to layer 2.

The samples were then processed according to Example 1 exposed, processed and irradiated with a xenon lamp. The measured percentage decreases in density are reproduced in Table 2.

In addition, exposed and processed samples were 5 weeks in the heating cabinet at 80 ° C and 50% rel. Moisture stored, and then the veil and the percentage decrease in density at D _max determined. The results are shown in Table 3. sample stabilizer Co-stabilizer Density decrease in% at density 0.5 1.0 1.5 1 (compare) - - 55 30th 42 2 " X-1 - 31 18th 15 3 " X-2 - 52 25th 22 4 (req.) I-4 - 16 7 6 5 " I-6 - 18th 9 8th 6 " I-14 - 20th 10th 10th 7 " I-21 - 21 10th 11 8th " I-25 - 17th 7 6 9 (compare) X-1 III-4 28 17th 14 10 (req.) I-4 III-4 13 5 4th 11 " I-4 V-2 12th 5 4th 12 " I-25 IV-2 15 5 5 13 " I-25 V-5 13 4th 4th

As Table 2 shows, the light stability of the yellow dye is significantly improved by the compounds essential to the invention compared to X-1 and X-2. With the addition of co-stabilizers of formulas III, IV and V, the light stability can be further improved. sample veil % Decrease in density gb pp bg 1 (compare) 22 15 11 11 2 " 21 14 11 10th 3 " 23 16 12th 12th 4 (req.) 16 12th 10th 6 5 " 17th 13 10th 7 6 " 18th 13 10th 7 7 " 18th 13 11 7 8th " 17th 12th 10th 6 9 (compare) 21 14 11 10th 10 (req.) 15 12th 20th 5 11 " 13 10th 8th 3rd 12 " 16 12th 9 6 13 " 13 10th 9 3rd

As Table 3 shows, the darkfading stability improved by the compounds essential to the invention. The Compounds X-1 and X-2 used as a comparison cause less improvement. The addition of Compounds of formula III, IV and especially V brings about a further improvement in darkfading stability.

Claims (5)

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 customary non-light-sensitive layers, characterised in that at least one layer contains a compound of the formula (I)

   

   in which

   X

   means -NH-, -NR- or -O-,

   R

   means alkyl, cycloalkyl or aryl,

   R₁

   means a chemical bond or a divalent bridging member,

   R₂ and R₃

   mean alkyl, alkoxy, alkenyl, cycloalkyl, aryl or aryloxy, or two residues R₂ or R₃ mean the remaining atoms of a benzene ring condensed with the phenyl residue and

   m and n

   mean 0 to 3, wherein all alkyl, alkoxy, cycloalkyl, alkenyl, aryl and aryloxy residues may be further substituted and in each of the two phenyl residues a residue R₁, R₂ or R₃ is in para position relative to the oxygen atom.

2. Colour photographic material according to claim 1, characterised in that the compound of the formula I is used in the yellow-coupling blue-sensitive layer, of which there is at least one, in a quantity of 0.1 to 2 mol/mol of coupler.
3. Colour photographic silver halide material according to claim 1, characterised in that the yellow coupler is a 2-equivalent pivaloyl coupler, the leaving group of which is attached to the coupling position either with oxygen or with nitrogen.
4. Colour photographic silver halide material according to claim 1, characterised in that the silver halide emulsions are at least 80 mol% AgCl emulsions.
5. Colour photographic silver halide material according to claim 1, characterised in that at least one compound of the formulae (III), (IV) and (V) is additionally used,

   

   in which

   Y

   means a residue which may be cleaved under chromogenic development conditions,

   R³¹

   means alkyl, cycloalkyl, acylamino, sulphonamino,

   R³², R³³, R³⁴

   mean H, alkyl, cycloalkyl, hydroxy, acyloxy, alkoxycarbonyl, halogen, acylamino, carbamoyl,

   R³⁵

   means alkyl, cycloalkyl, alkoxycarbonyl, acylamino, carbamoyl and two adjacent residues R³¹ to R³⁵ may form a 5- or 6-membered ring;

   

   in which

   R⁴¹

   means H, OH, alkoxy, aryloxy, acyl, acyloxy, alkyl, cycloalkyl,

   R⁴², R⁴³

   mean H, alkyl,

   R⁴⁴, R⁴⁵

   mean alkyl, cycloalkyl,

   Z

   means a group to complete a non-metallic 5- to 8-membered ring, wherein
   the residues R⁴² and R⁴⁵, R⁴³ and R⁴⁴, R⁴¹ and R⁴⁴ or R⁴⁵ may form a 5- to 8-membered ring. R⁵¹-S-R⁵² in which

   R⁵¹, R⁵² mean alkyl, cycloalkyl, aryl and the residues R⁵¹ and R⁵² may form a 5- to 8-membered ring.