EP0987593A1 - Colour photographic material - Google Patents

Abstract

The red spectrally-sensitized Ag halide emulsion layer of a color photographic material contains: (A) a substituted pyrazolo-azole cyan coupler and (B) a p-hydroxy-substituted diphenylsulfone coupler solvent. (A) is of formula (I) and (B) is of formula (II): R<11> and R<12> = electron-withdrawing groups; X<11> = H or a group splitting off on reaction with a developer oxidation product; Y<11> = a group completing an N-containing heterocyclic ring with the proviso that R<12> is a group bonded to a carbon atom of the heterocycle; n = 1 or 2; R<21> = alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, acyl, acylamino, acyloxy, hetaryl, halogen, NO2 or CN; R<22> = OH or as for R<21>; n</> and m = 0 or 1; o = 0, 1, 2, 3, 4 or 5; and p is not defined

Description

The invention relates to a color photographic material with an emulsified heterocyclic Teal couplers from the group of pyrazolo-azoles and certain Coupler solvents.

It is known to produce color photographic images by chromogenic development, i.e. by imagewise exposed silver halide emulsion layers in the presence of suitable color couplers using suitable color-forming Developer substances - so-called color developers - developed, which in accordance Oxidation product of the developer substance resulting with the silver image reacts with the color coupler to form a dye image.

To produce the blue-green partial image, naphtholic ones are usually used or phenolic cyan couplers. In color photographic supervisory materials So far, the latter has been given preference because of the more favorable absorption (at approx. 660 nm) and greater dark storage stability from them in the chromogenic Development generated image dyes.

However, the dark storage stability compared to that from the usual Pivaloylacetanilide yellow couplers and pyrazolotriazole purple couplers produced image dyes insufficient. Furthermore, the phenolic cyan dyes have one relatively large half-value range, which leads to a clear, undesirable absorption in the green spectral range.

To overcome these disadvantages, i.a. in EP 717 315 the use of specially substituted Pyrazoloazole proposed as a cyan coupler. The one from these Dyes produced in couplers show in the usual coupler solvents an absorption edge undesirably shifted to shorter wavelengths. On Another disadvantage is the insufficient light stability.

The object of the present invention was to use color photographic materials To provide pyrazolo-azole-cyan couplers that improved through Characterize light stability and at the same time have stability against heat. A Another task was to provide cyan couplers, their color rendering compared to the materials known from the prior art is improved.

in der

R¹¹ und R¹²

unabhängig voneinander für eine elektronenziehende Gruppe stehen,

X¹¹

für H oder eine bei der Reaktion mit Entwickleroxidationsprodukt abspaltbare Gruppe steht,

Y¹¹

für eine Gruppe zur Vervollständigung eines stickstoffhaltigen Heterocyclus steht, mit der Maßgabe, daß eine durch R¹² dargestellte Gruppe an ein Kohlenstoffatom des Heterocyclus gebunden ist,

n

für 1 oder 2 steht,

und mindestens eine Verbindung der Formel (II)

in der

R²¹

für Alkyl, Alkenyl, Aryl, Alkoxy, Aryloxy, Alkylamino, Arylamino, Acyl, Acylamimo, Acyloxy, Hetaryl, Halogen, Nitro oder Cyano steht,

R²²

für OH steht oder die gleiche Bedeutung hat wie R²¹,

n, m

unabhängig voneinander für 0 oder 1 stehen,

o

für 0, 1, 2, 3, 4 oder 5 steht, mit der Maßgabe, daß die Verbindung insgesamt mindestens 16 C-Atome enthält,

enthalten ist.The present invention relates to a color photographic material containing at least one silver halide emulsion layer which is sensitized to the red spectral range and assigned at least one compound of the formula (I)

in the

R ¹¹ and R ¹²

independently represent an electron-withdrawing group,

X ¹¹

represents H or a group which can be split off in the reaction with developer oxidation product,

Y ¹¹

represents a group for completing a nitrogen-containing heterocycle, with the proviso that a group represented by R ¹² is bonded to a carbon atom of the heterocycle,

n

represents 1 or 2,

and at least one compound of the formula (II)

in the

R ²¹

represents alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, acyl, acylamimo, acyloxy, hetaryl, halogen, nitro or cyano,

R ²²

represents OH or has the same meaning as R ²¹ ,

n, m

independently represent 0 or 1,

O

stands for 0, 1, 2, 3, 4 or 5, with the proviso that the compound contains a total of at least 16 carbon atoms,

is included.

Alkyl or linear in the sense of the present application are linear or branched straight-chain or cyclic, substituted or unsubstituted hydrocarbon groups to understand, preferably it is alkyl groups with 1 to 32 carbon atoms. Open-chain alkyl groups include, in particular, methyl, ethyl, n-propyl, n-butyl, n-octyl, n-dodecyl, n-hexadecyl and n-octadecyl and as branched Alkyl radicals, in particular 2-hexyl-decyl, 2-octyldodecyl and 2-ethylhexyl radicals in question. Among the cycloalkyl groups are cyclohexyl, in particular 4-t-butylcyclohexyl, 2,6-di-t-butyl-4-methyl-cyclohexyl preferred. Under alkenyl in For the purposes of the present application, linear or branched cyclic or straight chain substituted or unsubstituted unsaturated hydrocarbon radicals to understand such as ethenyl, 2-propenyl, isopropenyl and oleyl. Under Aryl in the sense of the present application are aromatic hydrocarbons understand, it is preferably phenyl or naphthyl. This can be both substituted and unsubstituted. Under hetaryl in the sense of In the present application, aromatic systems are to be understood, which at least contain a heteroatom. It is also preferably 5- or 6-membered Ring systems, which are monocyclic but also as condensed ring systems can be present. It can be both substituted and act unsubstituted ring systems. In particular come as heteroatoms N, S and O in question. A ring system can preferably be between 1 and 3 Have heteroatoms, which are the same or different heteroatoms can act. With the condensed ring systems, several of the same can be used or various heterocyclic systems can be condensed, as well as hetaryls Arylene. Typical examples are: pyridine, pyridazine, pyrimidine, pyrazine, oxazole, Isoxazole, thiazole, 3,4-oxdiazole, 1,2,4-oxdiazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, especially furan, pyrrole, thiophene and indole.

Alkoxy in the sense of the present application includes residues of the formula OR ' understand, wherein R 'for an alkyl radical according to the above. Definition stands.

Aryloxy in the sense of the present application includes residues of the type OR '' understand, in which R '' for an aryl radical as defined above stands.

Acyl in the sense of the present application can be an aliphatic, olefinic or aromatic carbon, carbon, carbamine, sulfone, amidosulfone, Act sulfinic, phosphoric, phosphonic or phosphonic acid residue.

Aryl, alkyl, Alkoxy, aryloxy, acyl, acyloxy, acylamino, hetaryl, alkynyl, hydroxy, cyano, Carboxy, sulfo and halogen such as preferably fluorine, chlorine or bromine in question.

Among an electron-withdrawing group in the sense of the present application is an optionally substituted carboxy, carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, halogenated aryloxy, aryloxy, acyl, sulfonyl, sulfinyl, Sulfonyloxy, sulfonylmethyl, sulfamoyl, tetrazolyl, pyrrolyl, phosphonyl, halogenated alkyl, halogenated aryl, cyano, alkylsulfonylmethyl, arylsulfonylmethyl or a nitro group, and a halogen atom.

Splitting groups X ₁₁ can be halogen, for example chlorine, N-linked, optionally substituted N-heteroaromatics, for example pyrrazoles, imidazole, triazoles or non-aromatic heterocycles, for example hydantoins, oxazolidinediones, S-linked aliphatic or aromatic mercaptans, for example mercaptopropionic acid, 2-acylaminophenyl mercaptane act over 0 linked aliphatic or aromatic hydroxy compounds, for example ethylene glycol, p-salicylic acid ethyl ester.

in der

R¹³ und R¹⁴

unabhängig voneinander die Bedeutung von R¹¹ bzw. R¹² haben,

X₁₂

die Bedeutung von X₁₁ hat und

Z₁₂

für H oder einen Substituenten steht.

Compounds of the formula (I) used with preference are those of the formula (IA)

in the

R ¹³ and R ¹⁴

independently of one another have the meaning of R ¹¹ or R ¹² ,

X ₁₂

has the meaning of X ₁₁ and

Z ₁₂

represents H or a substituent.

in der

R²³, R²⁴

unabhängig voneinander für Alkyl, Acyl, Acylamino, Alkoxy, Halogen, Cyano oder Nitro stehen,

R²⁵

für H oder Alkyl steht,

R²⁶

für H, Alkyl oder Acyl steht und

r, s

unabhängig voneinander für 0, 1 oder 2 stehen.

In the compounds of formula (II), R ²¹ preferably represents alkyl, alkoxy, alkylamino, acyl, acylamino, acyloxy, hydroxy or halogen, n and m preferably represent 0 or 1, with the proviso that n and m are not 1 at the same time are, o for zero, 1 or 2 and p for zero, 1, 2 or 3. Particularly preferred compounds of the formula (II) are those of the formula (II-A)

in the

R ²³ , R ²⁴

independently of one another represent alkyl, acyl, acylamino, alkoxy, halogen, cyano or nitro,

R ²⁵

represents H or alkyl,

R ²⁶

represents H, alkyl or acyl and

r, s

independently represent 0, 1 or 2.

Some particularly preferred compounds of the formula (I) or (IA) are listed by way of example in Table 1 below.

The following are some examples of the invention which are particularly preferred according to the invention Formula (II) or (II-A) listed.

Examples of compounds of the formula (II) according to the invention are

The compounds of the formula (I) and (II) according to the invention can be used in the usual amounts in the photographic material. The compounds of formula (I) are preferably used with 20 to 2,000 mg / m ^{2 of} the photographic material, in particular 50 to 500 mg / m ^{2 of} the photographic material. The compounds of the formula (II) are preferably used in a weight ratio of 20: 1 to 1:10 to compounds of the formula (I), in particular in a weight ratio of 10: 1 to 1: 5 and particularly preferably in a weight ratio of 5: 1 to 1: 2.

The compounds of the formulas (I) and (II) according to the invention are preferably in a red-sensitized silver halide emulsion layer or directly adjacent used for a red-sensitized silver halide emulsion layer. In particular the compounds of the formulas (I) and (II) are used in the same layer.

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. An overview can be found in Research Disclosure 37038 (1995) and Research Disclosure 38957 (1996).

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. Suitable as a carrier especially thin films and foils. An overview of carrier materials and auxiliary layers applied on the front and back are in Research Disclosure 37254, Part 1 (1995), p. 285 and in Research Disclosure 38957, Part XV (1996), p. 627.

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

Depending on the type of photographic material, these layers can vary be arranged. This is shown for the most important products:

Color photographic films such as color negative films and color reversal films show in the the following sequence on the carrier 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers. The layers are the same spectral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers usually closer to Carriers are arranged than the more sensitive sub-layers.

Between the green sensitive and blue sensitive layers is common a yellow filter layer is applied, which prevents blue light from penetrating into the one below Layers.

The possibilities of the different layer arrangements and their effects on the photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183-193 and in Research Disclosure 38957 Part XI (1996), p. 624 described.

Color photographic paper, which is usually much less sensitive to light as a color photographic film, points in the order given below usually a blue-sensitive, yellow-coupling silver halide emulsion layer on the support, a green sensitive, purple coupling silver halide emulsion layer and a red sensitive, cyan-coupling silver halide emulsion layer on; the yellow filter layer can be omitted.

Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low-sensitive layers Layers combined into another layer package in a photographic film be to increase the sensitivity (DE-25 30 645).

Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37254, part 2 (1995), p. 286 and in Research Disclosure 38957, Part II.A (1996), p. 598.

Information about suitable silver halide emulsions, their preparation, maturation, Stabilization and spectral sensitization including suitable spectral sensitizers can be found in Research Disclosure 37254, Part 3 (1995), p. 286, in Research Disclosure 37038, Part XV (1995), p. 89 and in Research Disclosure 38957, Part V.A (1996), p. 603.

Photographic materials with camera sensitivity usually contain silver bromoiodide emulsions, which may also contain small amounts of silver chloride can contain. Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% of AgBr or silver chloride bromide emulsions over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288, in Research Disclosure 37038, Part II (1995), p. 80 and in Research Disclosure 38957, Part X.B (1996), p. 616. The maximum absorption of the dyes formed from the couplers and the color developer oxidation product is preferably in the following ranges: yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan couplers 630 to 700 nm.

Color photographic films are used to improve sensitivity, royalty, Sharpness and color separation are often used in the compounds in the reaction with the developer oxidation product release compounds that are photographic are effective, e.g. DIR couplers that release a development inhibitor.

Information on such compounds, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290, in Research Disclosure 37038, Part XIV (1995), p. 86 and in Research Disclosure 38957, Part X.C (1996), p. 618.

The mostly hydrophobic color coupler, but also other hydrophobic components of the Layers are usually found in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in one emulsified aqueous binder solution (usually gelatin solution) and lie after drying the layers as fine droplets (0.05 to 0.8 µm diameter) in the layers before.

Suitable high-boiling organic solvents, methods for incorporation into the Layers of photographic material and other methods, chemical compounds Research can be found in photographic layers Disclosure 37254, Part 6 (1995), p. 292.

The usually arranged between layers of different spectral sensitivity non-photosensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive in another light-sensitive layer with different spectral Prevent awareness.

Suitable connections (white coupler, scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292, in Research Disclosure 37038, Part III (1995), p. 84 and in Research Disclosure 38957, part X.D (1996), p. 621 ff.

The photographic material can also UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _Min dyes, plasticizers (latices), biocides and additives to improve the coupler and dye stability, to reduce the color fog and for Reducing yellowing and other included. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292, in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff and in Research Disclosure 38957, parts VI, VIII, IX and X (1996), pp. 607 and 610 ff.

The layers of color photographic materials are usually hardened, i.e. that Binder used, preferably gelatin, is replaced by suitable chemical Process networked.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), P. 294, in Research Disclosure 37038, Part XII (1995), p. 86 and in Research Disclosure 38957, Part II.B (1996), p. 599.

After photographic exposure, color photographic materials become their character processed according to different processes. Procedural details and chemicals required for this are in Research Disclosure 37254, Part 10 (1995), p. 294, in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), p. 630 ff published together with exemplary materials.

in der

R³¹

für H, Alkyl, Alkenyl, Aryl oder Acyl steht,

R³²

für H, Alkyl, Alkoxy, Aryloxy, Acylamino, Alkylamino, Arylamino, Hydroxy oder Hetaryl steht und

R³³

H, Alkyl, Alkenyl, Aryl, Acyl oder Chlor steht.

wobei mehrere Reste R³² und R³³ gleich oder verschieden sein können.Compounds of the formula (III) are preferably used as dye stabilizers

in the

R ³¹

represents H, alkyl, alkenyl, aryl or acyl,

R ³²

represents H, alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl and

R ³³

H, alkyl, alkenyl, aryl, acyl or chlorine.

where several R ³² and R ^{33 may be the} same or different.

Typical examples of compounds of the formula (III) are

The compounds of the formula (III) are preferably used together with the Compounds of formulas (I) and (II) used in the same layer.

example Layer structure 1

Schicht 1:

(Substratschicht) 0,10g Gelatine

Schicht 2:

(blauempfindliche Schicht)
blausensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Komdurchmesser 0,9 µm) aus 0,46 g AgNO₃, mit 0,70 mg Blausensibilisator BS-1 0,30 mg Stabilisator ST-1 1,25 g Gelatine 0,48 g Gelbkuppler Y-1 0,20 g Bildstabilisator BST-1 0,50 g Ölbildner OF-1

Schicht 3:

(Zwischenschicht) 1,10g Gelatine 0,06 g EOP-Fänger EF-1 0,06 g EOP-Fänger EF-2 0,12 g Trikresylphosphat (TKP)

Schicht 4:

(grünempfindliche Schicht)
grünsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,47 µm) aus 0,26 g AgNO₃, mit 0,70 mg Grünsensibilisator GS-1 0,50 mg Stabilisator ST-2 0,77 g Gelatine 0,24 g Purpurkuppler M-1 0,20 g Bildstabilisator BST-2 0,09 g Bildstabilisator BST-3 0,24 g Dibutylphthalat (DBP) 0,24 g Isotetradecanol

Schicht 5:

(UV-Schutzschicht) 0,95 g Gelatine 0,50 g UV-Absorber UV-1 0,03 g EOP-Fänger EF-1 0,03 g EOP-Fänger EF-2 0.15 g Ölbildner OF-2 0,15g TKP

Schicht 6:

(rotempfindliche Schicht)
rotsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,30 g AgNO₃, mit 0,03 mg Rotsensibilisator RS-1 0,60 mg Stabilisator ST-3 1,00 g Gelatine 0,35 g Blaugrünkuppler C-1 0,70 g Dibutyladipat

Schicht 7:

(UV-Schutzschicht) 0,30 g Gelatine 0,20 g UV-Absorber UV-2 0,10 g Ölbildner OF-3

Schicht 8:

(Schutzschicht) 0,90 g Gelatine 0,05g Weißtöner WT-1 0,07 g Beize (Polyvinylpyrrolidon) 1,20 mg Silikonöl 2,50 mg Abstandshalter (Polymethylmethacrylat, mittlere Teilchengröße 0,8 µm) 0,30 g Härtungsmittel H-1

A color photographic recording material 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 1:

(Substrate layer) 0.10g gelatin

Layer 2:

(blue sensitive layer)
Blue-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.9 µm) from 0.46 g AgNO ₃ , with 0.70 mg Blue sensitizer BS-1 0.30 mg Stabilizer ST-1 1.25 g gelatin 0.48 g Yellow coupler Y-1 0.20 g Image stabilizer BST-1 0.50 g Oil former OF-1

Layer 3:

(Intermediate layer) 1.10g gelatin 0.06 g EOP catcher EF-1 0.06 g EOP catcher EF-2 0.12 g Tricresyl phosphate (CPM)

Layer 4:

(green sensitive layer)
green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.47 µm) from 0.26 g AgNO ₃ , with 0.70 mg Green sensitizer GS-1 0.50 mg Stabilizer ST-2 0.77 g gelatin 0.24 g Purple coupler M-1 0.20 g Image stabilizer BST-2 0.09 g Image stabilizer BST-3 0.24 g Dibutyl phthalate (DBP) 0.24 g Isotetradecanol

Layer 5:

(UV protective layer) 0.95 g gelatin 0.50 g UV absorber UV-1 0.03 g EOP catcher EF-1 0.03 g EOP catcher EF-2 0.15 g Oil former OF-2 0.15g 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) from 0.30 g AgNO ₃ , with 0.03 mg Red sensitizer RS-1 0.60 mg Stabilizer ST-3 1.00 g gelatin 0.35 g Teal coupler C-1 0.70 g Dibutyl adipate

Layer 7:

(UV protective layer) 0.30 g gelatin 0.20 g UV absorber UV-2 0.10 g Oil generator OF-3

Layer 8:

(Protective layer) 0.90 g gelatin 0.05g White toner WT-1 0.07 g Stain (polyvinylpyrrolidone) 1.20 mg Silicone oil 2.50 mg Spacers (polymethyl methacrylate, average particle size 0.8 µm) 0.30 g Hardener H-1

Connections used in layer structure 1:

Layer structures 2 to 10

The layer structures 2 to 10 correspond in layer structure and composition to layer structure 1 and differ only in that the cyan coupler C-1 and TKP in layer 6 were replaced by the substances specified in Table 1. In addition, for samples 4, 9 and 10, the silver application was reduced to 0.30 g / m ² .

a) Farbentwickler - 45 s-35°C Tetraethylenglykol 20,0 g N,N-Diethylhydroxylamin 2,0 g N,N-Bis-(2-sulfoethyl)hydroxylamindinatriumsalz 2,0 g N-ethyl-N-(2-methansulfonamidoethyl)-4-amino-3-methylbenzol-sulfat 5,0 g Kaliumsulfit 0,2 g Kaliumcarbonat 30,0 g Hydroxyethandiphosphonsäure 0,2 g Polymaleinsäureanhydrid 2,5 g Weißtöner (4,4'-Diaminstilbensulfonsäure-Derivat) 2,0 g Kaliumbromid 0,02 g auffüllen mit Wasser auf 1 000 ml; pH-Wert mit KOH oder H₂SO₄ auf pH 10,2 einstellen.

b) Bleichfixierbad - 45 s - 35°C Ammoniumthiosulfat 75,0g Natriumhydrogensulfit 13,5 g Ethylendiamintetraessigsäure (Eisen-Ammonium-Salz) 45,0 g auffüllen mit Wasser auf 1 000 ml; pH-Wert mit Ammoniak (25 Gew.-%) oder Essigsäure auf pH 6,0 einstellen.

c) Wässern - 90s - 33°C

d) Trocknen Anschließend wurde die Maximaldichte (D_max) und die Gradation (γ) gemessen (Tabelle 2). Außerdem wurde die prozentuale Purpurdichte (Nd_pp) bei D_bg = 1,0 sowie das Absorptionsmaximum (λ_max) ermittelt (Tabelle 2).Weiterhin wurden die Proben dem Licht einer auf Tageslicht normierten Xenonlampe ausgesetzt und mit 10·10⁶ lux·h bestrahlt. Es wurde der prozentuale Dichterückgang bei der Anfangsdichte D_bg = 1,0 bestimmt (▵D_1,0, Tabelle 2).Desweiteren wurden die Proben 42 Tage bei 85°C und 60 % rel. Feuchte dunkel gelagert und der prozentuale Rückgang der Maximaldichte (D_max) bestimmt (Tabelle 2).

(V = Vergleich; E = erfindungsgemäß) Schichtaufbau Kuppler Ölformer Verbindung mg/m² mg/m² 1 (V) C-1 350 TKP 700 2 (V) I-8 300 TKP 600 3 (V) I-8 300 V-1 / TKP 400 / 200 4 (V) I-3 300 V-2 600 5 (E) I-8 300 II-1 / TKP 400 400 / 200 6 (E) I-8 300 II-7 600 7 (E) I-8 300 II-13 600 8 (E) I-8 300 II-14 600 9 (E) I-3 300 II-13 600 10 (E) I-3 300 II-19 / TKP 400 / 200 (V = Vergleich; E = erfindungsgemäß) Schichtaufbau Nr. Sensitometrie Farbwiedergabe Lichtstabilität Dunkellagerstabilität D_max γ λ_max [nm] Ndpp [%] ▵D_1,0, [%] ▵D_max [%] 1 (V) 2,50 3,71 660 26,5 -16 -46 2 (V) 2,55 3,47 650 31,7 -34 -42 3 (V) 2,58 3,66 654 27,2 -26 -35 4 (V) 2,61 3,64 652 30,0 -31 -39 5 (E) 2,55 3,70 659 23,4 -20 -31 6 (E) 2,58 3,68 658 24,2 -21 -29 7 (E) 2,65 3,75 659 23,3 -17 -30 8 (E) 2,59 3,72 660 22,8 -19 -32 9 (E) 2,68 3,88 661 21,9 -17 -28 10 (E) 2,60 3,69 659 23,9 -20 -30 The samples were exposed through a step wedge, with color filters being introduced into the beam path in such a way that only the red-sensitive layer was exposed. It was then processed as follows:

a) Color developer - 45 s-35 ° C Tetraethylene glycol 20.0 g N, N-diethylhydroxylamine 2.0 g N, N-bis (2-sulfoethyl) hydroxylamine disodium salt 2.0 g N-ethyl-N- (2-methanesulfonamidoethyl) -4-amino-3-methylbenzene sulfate 5.0 g Potassium sulfite 0.2 g Potassium carbonate 30.0 g Hydroxyethane diphosphonic acid 0.2 g Polymaleic anhydride 2.5 g White toner (4,4'-diaminstilbenesulfonic acid derivative) 2.0 g Potassium bromide 0.02 g make up to 1,000 ml with water; Adjust pH to pH 10.2 with KOH or H ₂ SO ₄ .

b) bleach-fix bath - 45 s - 35 ° C Ammonium thiosulfate 75.0g Sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (iron ammonium salt) 45.0 g make up to 1,000 ml with water; Adjust the pH to 6.0 with ammonia (25% by weight) or acetic acid.

c) Soak - 90s - 33 ° C

d) Drying Then the maximum density (D _max ) and the gradation (γ) were measured (Table 2). In addition, the percent purple density (Nd _pp ) at D _bg = 1.0 and the absorption maximum (λ _max ) were determined (Table 2). Furthermore, the samples were exposed to the light of a xenon lamp normalized to daylight and with 10 · 10 ⁶ lux · h irradiated. The percentage density decrease at the initial density D _bg = 1.0 was determined (▵D _1.0 , Table 2). Furthermore, the samples were 42 days at 85 ° C and 60% rel. Moisture stored dark and the percentage decrease in maximum density (D _max ) determined (Table 2).

(V = comparison; E = according to the invention) Layer structure Coupler Oil former connection mg / m ² mg / m ² 1 (V) C-1 350 CPM 700 2 (V) I-8 300 CPM 600 3 (V) I-8 300 V-1 / TKP 400/200 4 (V) I-3 300 V-2 600 5 (E) I-8 300 II-1 / TKP 400 400/200 6 (E) I-8 300 II-7 600 7 (E) I-8 300 II-13 600 8 (E) I-8 300 II-14 600 9 (E) I-3 300 II-13 600 10 (E) I-3 300 II-19 / TKP 400/200 (V = comparison; E = according to the invention) Layer structure no. Sensitometry Colour reproduction Light stability Dark storage stability D _max γ λ _max [nm] Ndpp [%] ▵D _1.0 , [%] ▵D _max [%] 1 (V) 2.50 3.71 660 26.5 -16 -46 2 (V) 2.55 3.47 650 31.7 -34 -42 3 (V) 2.58 3.66 654 27.2 -26 -35 4 (V) 2.61 3.64 652 30.0 -31 -39 5 (E) 2.55 3.70 659 23.4 -20 -31 6 (E) 2.58 3.68 658 24.2 -21 -29 7 (E) 2.65 3.75 659 23.3 -17 -30 8 (E) 2.59 3.72 660 22.8 -19 -32 9 (E) 2.68 3.88 661 21.9 -17 -28 10 (E) 2.60 3.69 659 23.9 -20 -30

The following were used as comparative compounds

As Table 2 shows, the use of the couplers (I) according to the invention leads to compared to C-1 to a cyan image with improved dark storage stability.

However, the color rendering and light stability are unsatisfactory. Only at; only when simultaneous use of compounds of the formula (II) according to the invention is a satisfactory light stability and even significantly improved compared to C-1 Color rendering achieved.

Claims (10)

Color photographic material containing at least one silver halide emulsion layer sensitized to the red spectral range, assigned at least one compound of the formula (I)

in the

R ¹¹ and R ¹²

independently represent an electron-withdrawing group,

X ¹¹

represents H or a group which can be split off in the reaction with developer oxidation product,

Y ¹¹

represents a group for completing a nitrogen-containing heterocycle, with the proviso that a group represented by R ¹² is bonded to a carbon atom as a heterocycle,

n

represents 1 or 2,

and at least one compound of the formula (II)

in the

R ²¹

represents alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, acyl, acylamimo, acyloxy, hetaryl, halogen, nitro or cyano,

R ²²

represents OH or has the same meaning as R ²¹ ,

n, m

independently represent 0 or 1,

O

stands for 0, 1, 2, 3, 4 or 5, with the proviso that the compound has a total of at least 16 carbon atoms

contains. Color photographic material according to Claim 1, characterized in that the compounds of the formula (I) are the compounds of the formula (IA) shown below:

in the

R ¹³ and R ¹⁴

independently of one another have the meaning of R ¹¹ or R ¹² ,

X ₁₂

has the meaning of X ₁₁ and

Z ₁₂

represents H or a substituent.

Color photographic material according to one of claims 1 or 2, characterized in that in the compounds of formula (II)

R ²¹

represents alkyl, alkoxy, alkylamino, acyl, acylamine, acyloxy, hydroxy or halogen, and

n, m

independently represent 0 or 1 and

O

for 0, 1 or 2, as well

p

represents 0, 1, 2 or 3

Color photographic material according to one of Claims 1 to 3, characterized in that the compounds of the formula (II) are those of the formula (II-A):

in the

R ²³ , R ²⁴

independently of one another represent alkyl, acyl, acylamino, alkoxy, halogen, cyano or nitro,

R ²⁵

represents H or alkyl,

R ²⁶

represents H, alkyl or acyl and

r, s

independently represent 0, 1 or 2.

Color photographic material according to one of claims 1 to 4, characterized in that it contains the compound of formula (I) in an amount of 50 to 500 mg / m ^{2 of} the photographic recording material. Color photographic material according to one of claims 1 to 5, characterized characterized in that the compounds of formula (II) in a weight ratio from 20: 1 to 10: 1 for compound (I) are contained. Color photographic material according to one of claims 1 to 6, characterized in that it additionally contains compounds of the formula (III),

in the

R ³¹

represents H, alkyl, alkenyl, aryl or acyl,

R ³²

represents H, alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylamino, hydroxy or hetaryl and

R ³³

H, alkyl, alkenyl, aryl, acyl or chlorine.

where several R ³² and R ^{33 may be the} same or different. Color photographic material according to one of claims 1 to 7, characterized characterized in that the compounds of formulas (I) and (II) in a red-sensitized Silver halide emulsion layer or directly adjacent to a red-sensitized silver halide emulsion layer are included. Color photographic material according to one of claims 1 to 7, characterized characterized in that the compounds of formulas (I) and (II) in the same layer can be used. Color photographic material according to one of claims 1 to 7, characterized characterized in that the compounds of formulas (I), (II) and (III) in the same layer are included.