EP0871066A1 - Colour photographic silver halide material - Google Patents

Abstract

In colour photographic silver halide material with a base and silver halide emulsion layer(s), at least one layer contains a 3-(2-hydroxyphenyl)-benzofuran-2-one or its ether or ester of formula (I): R1 = hydrogen, alkyl or acyl; R2, R3 = (cyclo)alkyl, alkenyl, (het)aryl, halogen, OR4, SR5, NR6R7, nitro, cyano, SO2R8, COOR9 or COR10; R4, R5, R9 = (cyclo)alkyl, alkenyl or (het)aryl; R6, R7 = H, R4, COR10, COOR9 or SO2R8; R8, R10 = (cyclo)alkyl, alkenyl, (het)aryl or NR6R7; n, m - 0, 1, 2, 3 or 4; or 2 R2 and/or R3 groups = a group forming a condensed carbo- or heterocyclic ring; or (I) are linked to a polymer chain by R1, R2 or R3.

Description

The invention relates to a color photographic silver halide material with improved Characteristics.

a.) hohe Wirksamkeit, d.h. wirksame Vermeidung unerwünschter Mitkupplung,

b.) große Lagerstabilität, d.h. Vermeidung von Wirkungsverlusten durch Oxidation vor der Verarbeitung;

c.) keine Beeinträchtigung der Bildstabilität, d.h. bei Film z.B. Vermeidung der Nachkupplung, bei Papier z.B. Stabilität der Farbstoffe gegen Feuchte, Wärme und Licht.

The practical requirements for EOP-catchers (trapping reagents for the developer oxidation product) in color photographic silver halide materials (color film and color paper) are

a.) high effectiveness, ie effective avoidance of unwanted coupling,

b.) great storage stability, ie avoiding loss of effectiveness due to oxidation before processing;

c.) no impairment of the image stability, ie in the case of film, for example, avoidance of recoupling, in the case of paper, for example, stability of the dyes against moisture, heat and light.

So-called white couplers or redox-active are used to solve these tasks Connections used. These are usually pyrazolone couplers with a methyl group in the coupling site or around diffusion-resistant Hydroquinones, disulfonamidophenols and N-aryl-N'-acylhydrazine. These connections but can meet the requirements of practice as described above are not sufficiently fulfilled.

It has now been found that certain benzofuranones are surprising Make improvements.

worin

R₁

Wasserstoff, Alkyl oder Acyl,

R₂, R₃

unabhängig voneinander Alkyl, Cycloalkyl, Alkenyl, Aryl, Halogen, OR₄, SR₅, NR₆R₇, Nitro, Cyano, SO₂R₈, COOR₉, COR₁₀ oder Hetaryl,

R₄, R₅, R₉

unabhängig voneinander Alkyl, Cycloalkyl, Alkenyl, Aryl oder Hetaryl,

R₆, R₇

unabhängig voneinander H, R₄, COR₁₀, COOR₉, SO₂R₈ ,

R₈, R₁₀

unabhängig voneinander Alkyl, Cycloalkyl, Alkenyl, Aryl, Hetaryl oder NR₆R₇,

n, m 0, 1, 2, 3 oder 4

bedeuten oder 2 Reste R₂ bzw. R₃ jeweils einen ankondensierten carbo- oder heterocyclischen Ring bedeuten können oder die Verbindung der Formel I über einen der Reste R₁, R₂ oder R₃ an eine Polymerkette gebunden ist. Bevorzugt befindet sich mindestens einer der Reste R₂ und R₃ in para-Stellung zum phenolischen Sauerstoff.

The invention therefore relates to a color photographic silver halide material with a support and at least one light-sensitive silver halide emulsion layer,
which contains at least one compound of the general formula (I) in at least one layer:

wherein

R ₁

Hydrogen, alkyl or acyl,

R ₂ , R ₃

independently of one another alkyl, cycloalkyl, alkenyl, aryl, halogen, OR ₄ , SR ₅ , NR ₆ R ₇ , nitro, cyano, SO ₂ R ₈ , COOR ₉ , COR ₁₀ or hetaryl,

R ₄ , R ₅ , R ₉

independently of one another alkyl, cycloalkyl, alkenyl, aryl or hetaryl,

R ₆ , R ₇

independently of one another H, R ₄ , COR ₁₀ , COOR ₉ , SO ₂ R ₈ ,

R ₈ , R ₁₀

independently of one another alkyl, cycloalkyl, alkenyl, aryl, hetaryl or NR ₆ R ₇ ,

n, m 0, 1, 2, 3 or 4

mean or 2 radicals R ₂ or R _{3 can} each mean a fused-on carbo- or heterocyclic ring or the compound of formula I is bound to a polymer chain via one of the radicals R ₁ , R ₂ or R ₃ . At least one of the radicals R ₂ and R ₃ is preferably para to the phenolic oxygen.

Acyl residues R ₁ can be residues of an aromatic or aliphatic carboxylic, carbamic, carbonic, sulfonic, sulfinic or phosphoric acid.

The incorporation into a polymer chain can take place via an unsaturated group, for example a styrene, acrylic acid or methacrylic acid group. A suitable monomer is, for example

an ein Polymer gebunden werden:

Furthermore, the compound of formula I can be made to a polymer via a polymer-analogous reaction. For example, the following connection

be bound to a polymer:

In a preferred embodiment, R ₂ is R ₃ and n is m.

R _{1 is} preferably hydrogen or acyl, R ₂ and R _{3 are} alkyl, the sum of the C atoms in the alkyl radicals R ₂ and R _{3 being} 8 8. Preferred acyl residues are the residues of aromatic and aliphatic carboxylic acids.

Examples of compounds of the formula (I) in which R _{1 is} hydrogen are:

The position of the substituents relates to the oxygen. The position is 3 para-constant to the 2nd ring link.

Other examples are:

Preparation of compound I-4

To a mixture of 500 ml glacial acetic acid and 90 ml conc. 24.4 ml of an aqueous, 50% by weight oxoacetic acid and then 91.7 g of 4 - (1,1,3,3-tetramethylbutyl) phenol are added to sulfuric acid at room temperature.
After stirring overnight, the resulting precipitate is filtered off, washed with glacial acetic acid and then with water.
After drying, 81.1 g (90% of theory) of compound I-4 with a melting point of 125 to 127 ° C. are obtained.

The other compounds mentioned are obtained in a corresponding manner. If the reactivity of the phenolic component is reduced, it can be aggravated Reaction conditions become necessary e.g. by increasing the temperature, Increasing the concentration of sulfuric acid in the melt etc. Furthermore, all or part of the sulfuric acid can be replaced by other acids e.g. by p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, polyphosphoric acid, Phthalic acid, trifluoroacetic acid, boric acid and the like. Like.

Compounds of the formula I in which R _{1 is} an acyl radical can be prepared from the corresponding hydroxyl compounds by reaction with acid chlorides or acid anhydrides.

The compounds of formula (I) are preferably used in an amount of 5 to 1000 mg / m ² , in particular 10 to 500 mg / m ² .

The compounds of formula (I) can also be present as a salt (phenolate); as Cations are particularly suitable for metal cations and ammonium ions Alkali metal ions and trialkyl or tetraalkylammonium ions.

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.

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 to their front and back is in Research Disclosure 37254, Part 1 (1995), p. 285.

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 in the following order 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 same spectral sensitivity differ in their photographic sensitivity, with the less sensitive sub-layers usually closer arranged to the carrier than the higher sensitive sub-layers.

Between the green sensitive and blue sensitive layers is common a yellow filter layer is applied, which prevents blue light from entering the to get layers below.

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.

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 to another layer package in a photographic film be summarized to increase 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.

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), pp. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

Photographic materials with camera sensitivity usually contain silver bromide or iodide Silver bromide iodide chloride emulsions. Photographic copy materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption of that from the couplers and the color developer oxidation product Dyes formed are preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.

In color photography films, to improve sensitivity, Graininess, sharpness and color separation are often used in compounds React with the developer oxidation product to release compounds that are photographic are effective, e.g. DIR couplers that release a development inhibitor.

Information on such connections, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and in Research Disclosure 37038, Part XIV (1995), p. 86.

Mostly hydrophobic color couplers, but also other hydrophobic components of the layers, are usually 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 a photographic material and other methods, chemical Introducing connections into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

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

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

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 the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices), Contain biocides and others.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), P. 292 and in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff.

The layers of color photographic materials are usually hardened, i.e. the binder used, preferably gelatin, is by suitable cross-linked chemical processes.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), page 86.

After photographic exposure, color photographic materials become their character processed according to different processes. Details of the Procedures and chemicals required for this are in Research Disclosure 37254, part 10 (1995), p. 294 and in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff. Published together with exemplary materials.

The compounds of formula (I) are in particular in at least one neighboring layer to a green sensitive, containing at least one purple coupler Silver halide emulsion layer used, the silver halide emulsion is a silver bromide chloride emulsion with at least 95 mol% AgCl.

In this case, especially pyrazolotriazole purple couplers come as purple couplers into consideration.

example 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.

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
1.18 g gelatin
0.55 g yellow coupler Y-1
0.1 g white coupler W-1
0.2 g ST-1 dye stabilizer
0.29 g of oil former OF-1
0.10 g of oil former OF-2

Layer 3:

(Protective layer)
1.10 g gelatin
0.07 g of compound SC-1
0.07 g of compound SC-2
0.07 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 0.6 µm)
0.58 g of AgNO ₃ with
1.08 g gelatin
0.52 g purple coupler M-1
0.24 g ST-2 dye stabilizer
0.10 g ST-3 dye stabilizer
0.25 g dibutyl adipate
0.25 g isooctadecanol

Layer 5:

(UV protective layer)
1.15 g gelatin
0.2 g UV absorber UV-1
0.2 g UV absorber UV-2
0.2 g of oil former OF-3
0.07 g of compound SC-1
0.07 g of compound SC-2
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)
0.30 g AgNO ₃ with
0.75 g gelatin
0.2 g UV absorber UV-1
0.36 g of cyan coupler C-1
0.12 g ST-4 dye stabilizer
0.24 g CPM

Layer 7:

(UV protective layer)
0.35 g gelatin
0.15 g UV absorber UV-3
0.15 g of oil generator OF-4

Layer 8:

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

The following compounds were used in the layer structure of Example 1:

Samples 2 to 14

Samples 2 to 14 are prepared like sample 1 with the difference that in layers 2, 3, 4 and 5 the compounds Y-1, SC-1, SC-2 and M-1 are replaced by those given in table 1 . In addition, the silver coating in layer 4 was reduced to 0.28 g for samples 4 to 9 and to 0.22 g for samples 10 to 14. (V: comparison, E: according to the invention) [amount in mg / m ² ] Sample No. Layer 2 Layers 3 and 5 Layer 4 1 (V) Y -1 [550] SC -1 / SC -2 [70/70] M -1 [520] 2 (E) Y -1 [550] I - 1 [140] M -1 [520] 3 (E) Y -1 [550] I - 5 [140] M -1 [520] 4 (V) Y -1 / Y -2 [450/100] SC -1 / SC -2 [70/70] M -2 [250] 5 (V) Y -1 / Y -2 [450/100] SC -3 [140] M -2 [250] 6 (E) Y -1 / Y -2 [450/100] I - 4 [140] M -2 [250] 7 (E) Y -1 / Y -2 [450/100] I - 12 [140] M -2 [250] 8 (E) Y -1 / Y -2 [450/100] I - 24 [140] M -2 [250] 9 (E) Y -1 / Y -2 [450/100] I - 26 [140] M -2 [250] 10 (V) Y -3 [520] SC -2 [140] M -3 [140] 11 (V) Y -3 [520] SC -3 [140] M -3 [140] 12 (E) Y -3 [520] I - 9 [140] M -3 [140] 13 (E) Y -3 [520] I - 15 [140] M -3 [140] 14 (E) Y -3 [520] I - 28 [140] M -3 [140] 15 (E) Y -3 [520] I - 30 [150] M -3 [140]

One sample each was behind a gray wedge with blue, green and red light exposed and processed as follows:

a.) Color developer - 45 s - 35 ° C

Tetraethylene glycol 20.0 g N, N-diethylhydroxylamine 4.0 g N-ethyl-N- (2-methanesulfonamidoethyl) -4-amino-3-methylbenzene sulfate 5.0 g Potassium sulfite 0.2 g Potassium carbonate 30.0 g Polymaleic anhydride 2.5 g Hydroxyethane diphosphonic acid 0.2 g White toner (4,4'-diaminstilbenesulfonic acid derivative) 2.0 g Potassium bromide 0.02 g make up to 1000 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 75.0 g Sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (iron ammonium salt) 45.0 g make up to 1000 ml with water; pH value with ammonia (25%) or adjust acetic acid to pH 6.0.

c.) Soak - 2 min - 33 ° C d.) drying

The percentage bg density (D _bg ) at the pp density (D _pp ) 1.0 was then determined in the sample exposed to green light (Table 2). All samples were then exposed to the light of a xenon lamp normalized for daylight and irradiated with 15 · 10 ⁶ lux · h. The percentage decrease in density ΔD _gb , ΔD _pp and ΔD _bg after irradiation was determined at the initial density D = 1.0 (Table 2). Sample No. % D _bg at D _pp = 1.0 ΔD _gb [%] ΔD _pp [%] ΔD _bg [%] 1 (V) 10.1 -32 -28 -36 2 (E) 9.9 -23 -27 -27 3 (E) 9.8 -24 -27 -28 4 (V) 7.5 -34 -59 -35 5 (V) 8.6 -25 -34 -26 6 (E) 7.3 -22 -32 -27 7 (E) 7.6 -24 -32 -27 8 (E) 7.5 -23 -33 -26 9 (E) 7.2 -23 -34 -27 10 (V) 5.6 -44 -31 -35 11 (V) 6.3 -30 -16 -28 12 (E) 5.7 -28 -14 -26 13 (E) 5.4 -30 -15 -27 14 (E) 5.5 -29 -16 -27 15 (E) 5.4 -27 -15 -26

As Table 2 shows, the compounds of the invention effectively prevent that Coupling without adversely affecting the dye stability.

Compounds used for the first time in samples 2 to 14:

Example 2

A color photographic recording material for color negative development was produced (sample 15 - comparison) by applying the following layers in the order given to a transparent layer support made of cellulose triacetate with a thickness of 120 μm and having an adhesive layer. The amounts are given in g / m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application. All silver halide emulsions were stabilized per 100 g of AgNO ₃ with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetra-azaindene. The silver halide emulsions are characterized by the halide composition and in terms of grain size by the center of gravity (VSP). The center of volume has the dimension of a length [µm] and is determined by the relationship: VSP = Σ n i d i 4th Σn i d i 3rd where n _{i is} the number of particles in the interval i and d _{i is} the diameter of the balls of the same volume for the particles in the interval i. Layer: 1 (antihalo layer) black colloidal silver 0.28 UV absorber UV-2 0.20 gelatin 0.8 Layer: 2 (low-sensitivity red-sensitive layer) Red-sensitized silver bromide iodide chloride emulsion (2.4 mol% iodide; 10.5 mol% chloride; VSP 0.35) 0.85 gelatin 0.6 Teal Coupler C-2 0.3 colored coupler CR-1 2.0 x 10 ^-2 colored coupler CY-1 1.0 x 10 ^-2 DIR coupler DIR-1 1.0 x 10 ^-2 Layer: 3 (medium sensitive red sensitized layer) red-sensitized silver bromide iodide emulsion (10.0 mol% iodide; VSP 0.56) 1.2 gelatin 0.9 Teal Coupler C-2 0.2 colored coupler CR-1 7.0 x 10 ^-2 colored coupler CY-1 3.0 x 10 ^-2 DIR coupler DIR-1 4.0 x 10 ^-2 Layer: 4 (highly sensitive red-sensitized layer) red-sensitized silver bromide iodide emulsion (6.8 mol% iodide; VSP 1.2) 1.6 gelatin 1.2 Teal coupler C-3 0.15 DIR coupler DIR-3 3.0 x 10 ^-2 Layer: 5 (intermediate layer) gelatin 1.0 Layer: 6 (low-sensitivity green-sensitive layer) green-sensitized silver bromide iodide chloride emulsion (9.5 mol% iodide; 10.4 mol% chloride; VSP 0.5) 0.66 gelatin 0.9 Purple coupler M-4 0.3 colored coupler MY-1 2.0 x 10 ^-2 DIR coupler DIR-1 5.0 x 10 ^-3 DIR coupler DIR-2 1.0 x 10 ^-3 Oxform catcher SC-2 5.0 x 10 ^-2 Layer: 7 (medium-sensitive green-sensitized layer) green-sensitized silver bromide iodide chloride emulsion (10.0 mol% iodide; VSP 0.56) 1.4 gelatin 0.9 Purple coupler M-4 0.24 colored coupler MY-1 4.0 x 10 ^-2 DIR coupler DIR-1 5.0 x 10 ^-3 DIR coupler DIR 2 3.0 x 10 ^-3 Layer: 8 (highly sensitive green-sensitized layer) green-sensitized silver bromide iodide emulsion (6.8 mol% iodide; VSP 1.1) 1.7 gelatin 1.2 Purple coupler M-5 3.0 x 10 ^-2 colored coupler MY-2 5.0 x 10 ^-2 DIR coupler DIR-3 5.0 x 10 ^-2 Layer: 9 (intermediate layer) Polyvinyl pyrrolidone 10 ^-2 gelatin 0.4 Layer: 10 (yellow filter layer) yellow colloidal silver sol 0.1 gelatin 0.8 Layer: 11 (low-sensitivity blue-sensitized layer) Blue-sensitized silver bromide iodide emulsion (6.0 mol% iodide; VSP 0.78) 0.4 gelatin 1.0 Yellow coupler Y-4 0.4 DIR coupler DIR-1 3.0 x 10 ^-2 Layer: 12 (medium-sensitive blue-sensitized layer) Blue-sensitized silver bromide iodide chloride emulsion (8.8 mol% iodide; 15.0 mol% chloride; VSP 0.77) 0.12 (12.0 mol% iodide; 15.0 mol% chloride; VSP 1.0) 0.28 gelatin 0.77 Yellow coupler Y-4 0.58 Layer: 13 (highly sensitive blue sensitized layer) Blue-sensitized silver bromide iodide emulsion (12.0 mol% iodide; VSP 1.2) 1.2 gelatin 0.9 Yellow coupler Y-4 0.1 DIR coupler DIR-3 2.0 x 10 ^-2 Layer: 14 (protective layer) Mikrat - silver bromide iodide emulsion (4.0 mol% iodide; VSP 0.05) 0.25 UV absorber UV-4 0.2 UV absorber UV-2 0.3 gelatin 1.4 Layer: 15 (hardening layer) gelatin 0.2 Hardener H-1 0.86 Persoftal 0.04

Compounds used in Example 2:

The colorless and colored couplers were used together with the same Amount of tricresyl phosphate (CPM) according to the emulsification methods known in the art brought in.

Samples 16 to 18

Samples 16 to 18 differ from sample 15 in that they additionally contain compounds of the formula (I) (g / m ² ) in layer 1. The samples were then exposed to daylight behind a graduated gray wedge. The materials were then processed according to the process described in E. Ch. Gehret, The British J. of Photography 1974, p. 597. The relative red sensitivity and the bluish-green haze were measured from the samples obtained. The results are shown in Table 3. sample Connection in the 1st layer amount rel. Red Recommended Teal veil 15 - - 100 0.30 comparison 16 I - 4 0.200 123 0.21 according to the invention 17th I - 10 0.160 129 0.18 according to the invention 18th I - 27 0.250 123 0.20 according to the invention

Samples 19 through 24

Samples 19 to 24 differ from sample 15 in that an additional 0.125 mmol of the compounds listed in table 4 / m ^{2 were} used in layer 5. Samples 23 and 24 instead contained white couplers W-1 and W-2 in an amount of 0.125 mmol / m ² .

The samples were processed like samples 15 to 18. The purple density D ₁ at point E + logH after three days 'storage at 20 ° C and D ₂ after three days' storage at 60 ° C / 90% relative humidity were measured and the difference D ₂ -D ₁ and the purple haze (D _min ) after Storage at room temperature determined (E was determined at point 0.2 via fog). The results are shown in Table 4: sample connection D _min D ₂ -D ₁ 15 without 0.70 0.25 comparison 19th I - 4 0.48 0.20 according to the invention 20th I - 10 0.51 0.21 according to the invention 21 I - 25 0.51 0.23 according to the invention 22 I - 27 0.49 0.23 according to the invention 23 W - 1 0.50 0.68 comparison 24th W - 2 0.51 0.83 comparison

White coupler W 2 has the formula:

It can be seen from the results in Table 4 that the compounds according to the invention reduce the purple haze without the difference D ₂ -D ₁ increasing. The difference D ₂ -D ₁ is a measure of the stability of the developed image, since it allows statements about changing print conditions when storing the developed CN image.

Claims (7)

Color photographic silver halide material with a support and at least one silver halide emulsion layer, characterized in that in at least one layer at least one compound of the general formula (I)

wherein

R ₁

Hydrogen alkyl or acyl,

R ₂ , R ₃

independently of one another alkyl, cycloalkyl, alkenyl, aryl, halogen, OR ₄ , SR ₅ , NR ₆ R ₇ , nitro, cyano, SO ₂ R ₈ , COOR ₉ , COR ₁₀ or hetaryl,

R ₄ , R ₅ , R ₉

independently of one another alkyl, cycloalkyl, alkenyl, aryl or hetaryl,

R ₆ , R ₇

independently of one another H, R ₄ , COR _10, COOR ₉ , SO ₂ R ₈ ,

R ₈ , R ₁₀

independently of one another alkyl, cycloalkyl, alkenyl, aryl, hetaryl or NR ₆ R ₇ ,

n, m 0, 1, 2, 3 or 4

or 2 radicals R ₂ or R _{3 can} each represent a fused-on carbo- or heterocyclic ring or the compounds of the formula I are bonded to a polymer chain via one of the radicals R ₁ , R ₂ or R ₃ ,

is included. Color photographic silver halide material according to claim 1, characterized in that R _{1 is} hydrogen or acyl, R ₂ is R ₃ and m is n. Color photographic silver halide material according to Claim 1, characterized in that R _{1 is} hydrogen and R ₂ and R _{3 are} alkyl, the sum of the C atoms in the alkyl radicals R ₂ and R _{3 being} ≥ 8. Color photographic silver halide material according to claim 1, characterized in that the compounds of formula (I) are used in an amount of 5 to 1000 mg / m ² material. Color photographic silver halide material according to claim 1, characterized characterized in that it contains silver chloride bromide emulsions with over 95 mol% Contains AgCl. Color photographic silver halide material according to claim 5, characterized characterized in that the material at least one green sensitive, one Contains silver halide emulsion layer containing magenta couplers and the Compounds of formula (I) in at least one neighboring layer green sensitive silver halide emulsion layer is used. Color photographic silver halide material according to claim 6, characterized characterized in that the magenta coupler is a pyrazolotriazole magenta coupler is.