DE19902946A1 - Color photographic material, especially color negative film, contains selenium and/or tellurium in slow emulsion and smaller amount in faster emulsion of same spectral sensitivity - Google Patents

Abstract

In color photographic material with a base and >= 2 blue-, >= 2 green- and >= 2 red-sensitive silver halide (AgX) emulsion layers containing yellow, magenta and cyan couplers, in which >= 2 layers of the same spectral sensitivity and different speed contain selenium (Se) and/or tellurium (Te), the slow emulsion layer contains >= 1.3 times as much Se and/or Te as the faster layer, in terms of mole Se and/or Te/mole AgX.

Description

The invention relates to a color photographic silver halide material with a Carrier, at least two blue-sensitive silver halo containing yellow couplers genide emulsion layers, at least two green-sensitive, purple couplers ent holding silver halide emulsion layers and at least two red-sensitive, Silver halide emulsion layers containing cyan couplers, at least two silver halide emulsion layers photosensitive to the same color silver halide emulsion ripened with at least one selenium or tellurium compound included, which is characterized by an improved tropical stability.

It is known that spectrally sensitized emulsions become too sensitive can be ripened by the so-called chemical ripening alongside sulfur-donating compounds also selenium or tellurium-donating compounds applied to the surface of the silver halide crystals or selenium or tellurium releasing compounds are incorporated into the silver halide crystals.

From DE 197 19 842 it is known that there is a good sensitivity ratio maintains shelf life when within a color package of a photographic Material the more sensitive silver halide emulsion layer more selenium and / or tellurium than the lower sensitive layers.

The materials according to the prior art, however, have an insufficient tropical stability with regard to the filter differences (Dkop values). The filter differences are the density differences between the density measured behind the blue and the green filter (D _BG ) and between the density measured behind the red and the green filter (D _RG ). Changes to these filter differences during storage lead to color-incorrect prints and must therefore be as small as possible.

The object of the invention was therefore to develop and provide a material its filter differences hardly change during storage under tropical conditions change.

The object is achieved in that at least two for same color light-sensitive layers of different photographic sensitivity at least one silver halide emul containing selenium and / or tellurium sion and in the lower sensitive silver halide emulsion The amount of selenium and / or tellurium contained in the layer is at least 1.3 times that Amount of selenium and / or tellurium in the more sensitive silver halide emul sionsschicht, the amount in moles of selenium and / or tellurium per mole Silver halide of the layer in question is specified. In particular, the Amount 1.3 to 5 times.

Preferred embodiments of the invention can be found in the subclaims to take.

Heterocyclic selenones or tellurones come as selenium or tellurium ripening agents, in particular selenones, tri- or tetrasubstituted selenium or tellurea ureas, Phosphane selenides or tellurides with three ligands, which have carbon or O or N are connected to the phosphorus atom as heteroatoms, in particular tri arylphosphanselenide, diaryldiselenide or diarylditelluride; Arylselenoamides; Iso selenazolone; Arylselenocyanates with a polar group and cyclic Telluroether with a 5- to 7-membered ring in question.

Triarylphosphane selenides and cyclic telluroethers are preferred.

Suitable selenium and tellurium ripening agents can be found in DE 197 19 841, to which reference is hereby made.

The selenium and tellurium ripening agents are preferably used together with gold and sulfur compounds for ripening, e.g. B. with HAuCl ₄ , sodium thiosulfate and potassium thiocyanate, with gold compounds 10 ^-8 to 10 ^-4 mol / mol silver halide and sulfur compounds 10 ^-9 to 10 ^-1 mol / mol silver halide, in particular thiosulfate 10 ^-7 to 10 ^{- 5} mol / mol silver halide and 10 ^-7 to 10 ^-1 mol / mol silver halide of thiocyanate are used.

Suitable gold and sulfur compounds are EP-A 443 453 and the therein cited references can be found.

The selenium and tellurium ripening agents are preferred in amounts of 0.5 to 3 µmol / mol silver halide used.

The selenium and tellurium ripening is preferably carried out in the presence of a silver halide solvent. Examples of silver halide solvents are (a) organic thioethers, (b) thioureas, (c) compounds with a

-O-CS-N or -S-CS-N structure,

(d) imidazoles, (e) sulfites and (f) thiocyanates (US 3,271,157, 3,531,289, 3,574,628, JP-A 54-1 019, JP-A 54-158 917, JP-A 53-82 408, JP-A 55-77 737, JP-A 55-2 982, JP-A 53-144 319, JP-A 54-100 717).

Thiocyanates and tetramethylthiourea are preferred, which are used in particular in an amount of 10 ^-4 to 10 ^-2 mol per mol of silver halide.

The ripening with selenium and tellurium compounds is particularly, even if they are in Presence of sulfur and gold compounds is carried out at tempera doors above 35 ° C, preferably 45 to 90 ° C and at pH 4 to 9.

Spectral sensitizing dyes can be found in all common classes of sensitizers find, but preferably in the series of mono-, trimethine and pentamethine  cyanine dyes. Examples of these dyes are in Th. James, The Theory of the Photographic Process, 3rd edition (Macmillan 1966), pages 198-288.

The spectral sensitization and also the stabilization of the silver halide emuls ions can occur before, during and after chemical ripening.

The dyes can be silver halide for the entire range of visible Sensitize the spectrum. Particularly preferred dyes are the mono-, tri- and Pentamethine cyanines of benzoxazole, benzimidazole, benzothiazole, naphth oxazole, naphththiazole or benzoselenazole series, each in the benzene rings carry further substituents or further rings or ring systems as substituents or can wear in fused form, again among the pentamethine cyanines those whose methine part is part of a partially unsaturated ring. The Dyes can be cationic, uncharged in the form of betaines or sulfobetaines, or be anionic.

The ripened emulsions can be stabilized with heterocyclic NH or SH compounds in a known manner, in particular with those which have an acidic group, e.g. B. a -SO ₃ H or -COOH group. The stabilizers are added before the spectral sensitization and selected so that they do not displace the sensitizing dye or the sensitizing dyes from the silver halide crystals of the emulsion and also do not hinder the bleaching of the image silver in the course of processing.

Suitable stabilizers are:

The silver halide used can consist of silver chloride, silver bromide, silver chloride Freely selectable bromide, silver bromide iodide and silver bromide chloride iodide, it can also be epitaxial growth forms of Silver chloride on silver iodide or from silver iodide on silver chloride or silver act bromide chloride, the crystals can be homogeneous or zoned be inhomogeneous, it can be simple crystals, single or multiple twins Be crystals. The emulsions can consist of mostly compact, mostly rod-shaped or predominantly platelet-shaped crystals, they can also contain epitaxial growths. In the case of platelets Crystals with an aspect ratio above 3: 1 are preferred, those with a neighboring edge ratio close to 1 is particularly preferred.  

The emulsion crystals can also be doped with certain foreign ions influence the shape of the gradation, improve the stability of the latent image or the Affect the Schwarzschild effect, especially with multi-valued transition metal cations, e.g. B. with hexacyanoferrate (II) ions, hexacyanoruthenate (II) ions or with precious metal cations that are trivalent and have an octahedral ligand have surroundings, e.g. B. with ruthenium (III) -, rhodium (III) -, osmium (III) - or Iridium (III) salts, the function of the foreign ion doping essentially beyond that of a pure lattice fault and the installation of so-called targets flat electron traps.

The emulsions can be largely homodisperse or heterodisperse, you can accordingly by conventional precipitation, by one to more fold double enema or with the process of the microfilum solution become. They can also be so-called conversion emulsions.

The emulsions can also be ripened with reducing ripening agents. The Reduction ripening can also occur in the course of the precipitation of the emulsion crystals in depth of the crystal are built up, the reduction ripening nuclei in the further Growth of the crystals are covered. Two can be used as reducing agents valuable tin compounds, phosphane tellurides, N-aryl hydrazides, salts of the form amidine-C-sulfinic acid, boranates or other complex hydrides, but also macro cyclic polyamines and metal complexes made therefrom, used with advantage become. Organically soluble, quickly and completely adsorbable on the silver halide Reducing ripening agents are preferred.

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 silver color bleaching process. Color negative films are preferred.  

Thin films are particularly suitable as supports for the photographic materials and foils. An overview of carrier materials and on their front and back auxiliary layers applied in Research Disclosure 37254, Part 1 (1995), p. 285 shown.

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 of the same spec central sensitivity differ in their photographic sensitivity, the less sensitive sub-layers usually closer to the support are ordered 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 lying in the below layers.

The possibilities of the different layer arrangements and their out effects on the photographic properties are described in J. Int. Rec. Mats., 1994, Vol. 22, pages 183-193.

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-sensitivity layers layers into another layer package in a photographic film be set 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.

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

Photographic materials with camera sensitivity usually contain Sil berbromide iodide 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% 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. Die maximum absorption of the from the couplers and the color developer oxidation test Colored product dyes are preferably in the following ranges: yellow couplers 430 to 460 nm, magenta couplers 540 to 560 nm, cyan couplers 630 to 700 nm.

In color photographic films, to improve sensitivity, grainy speed, sharpness and color separation are often used in the compounds involved in the reaction with the developer oxidation product release compounds that are photographic are effective, e.g. B. 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 and in Research Disclosure 37038, Part XIV (1995), p. 86.  

The mostly hydrophobic color coupler, but also other hydrophobic components of the Layers are usually ge in high-boiling organic solvents dissolves or disperses. 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 through knife) in the layers.

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

The usually indicated between layers of different spectral sensitivity ordered non-photosensitive interlayers may contain agents that an undesirable diffusion of developer oxidation products from a light sensitive to another light-sensitive layer with different spectra Prevent central 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 UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _Min dyes, additives to improve the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices) , Biocide and others included.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), 5. 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 typically hardened, i.e. that is 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 and in Research Disclosure 37038, Part XII (1995), p. 86.

After photographic exposure, color photographic materials become their character processed according to different processes. Details on ver 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. Together with exemplary materials.  

Examples Emulsions used Emulsion Em A

A solution of 300 g of inert gelatin and 150.0 g of potassium was added to the batch kettle iodide placed in 15.0 kg of water with stirring. After heating to 65 ° C aqueous silver nitrate solution (2550 g silver nitrate in 11.25 kg water) and an aqueous one Halide solution (1763 g ammonium bromide in 5 kg water) within 15 Minutes dosed. The emulsion was then heated to 35 ° C. within 20 minutes cooled, flocculated at pH 3.5 by adding polystyrene sulfonic acid (PSS) and then washed at 20 ° C. The flocculate was then mixed with 4.0 kg of water filled and by adding 975 g of inert gelatin and 3.75 kg of water at pH 6.5 and redispersed at 50 ° C. The center of volume of the Ag (Br, I) emulsion was 0.45 µm, the distribution width 28% and the iodide content 6.0 mol%. You get platelet-shaped crystals with an aspect ratio of about 3.5: 1.

Emulsion Em B

A solution of 135 g of inert gelatin and 73.3 g of potassium was added to the batch kettle iodide placed in 6.0 kg of water with stirring. After heating to 79 ° C one aqueous silver nitrate solution (1500 g silver nitrate in 5 kg water) and an aqueous one Halide solution (1560 g ammonium bromide in 5 kg water) within Metered in 20 minutes. After a pause of 10 minutes at 79 ° C, the emul sion cooled to 20 ° C, flocculated at pH 3.5 by adding PSS and on finally washed at 20 ° C. The flocculate was then exposed to 4.0 kg of water filled and by adding 1365 g of inert gelatin and 3.5 kg of water at pH 6.5 and and a temperature of 50 ° C redispersed. The volume focus of the Ag (Br, I) emulsion was 1.0 µm, the distribution width 25% and the iodide content  5.0 mol%. Platelet-shaped crystals with an aspect ratio of about 4: 1.

Emulsion Em C

A solution of 135 g of inert gelatin and 22.0 g of potassium was added to the batch kettle iodide placed in 6.0 kg of water with stirring. After heating to 55 ° C one aqueous silver nitrate solution (1500 g silver nitrate in 9 kg water) and an aqueous one Halide solution (1560 g ammonium bromide in 9 kg water) within Metered in 20 minutes. After a pause of 10 minutes at 55 ° C, the emul cooled to 20 ° C, flocculated at pH 3.5 by adding PSS and then washed at 20 ° C. The flocculate was then mixed with 4.0 kg of water filled out and by adding 1365 g of inert gelatin and 3.5 kg of water at pH 6.5 and a temperature of 50 ° C redispersed. The volume focus of the Ag (Br, I) emulsion was 0.74 µm, the distribution width was 23% and the iodide content 1.5 mol%. Platelet-shaped crystals with an aspect ratio of about 5: 1.

For the production of emulsions Em A1 to Em A4, Em B1 to Em B4 and Em C1 to Em C4, the emulsion Em A, Em B and Em C at 53 ° C, a pH of 6.5 and a pAg of 8.5 optimally chemically matured. The ripening agents used for this quantities are listed in Table 1; tetrachloroauric acid was used as the gold compound used.

The following were used as selenium and tellurium compounds:

Table 1

To prepare the emulsions Em A1, Em A2 and Em B1 to Em B4 Emulsions Em A and Em B at 53 ° C, pH 6.5 and pAg 8.5 optimally chemically matured. The amounts of ripening agent used for this are shown in Table 1 listed, tetrachloroauric acid was used as the gold compound.  

Table 2

example 1

A color photographic recording material for color negative color development was produced (layer structure 1A) by applying the following layers in the order given to a transparent layer support made from cellulose triacetate. The quantities given relate to 1 m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application; the silver halides are stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO ₃ .

1st layer (antihalo layer)

0.3 g black colloidal silver
1.2 g gelatin
0.4 g UV absorber UV 1
0.02 g tricresyl phosphate (CPM)

2nd layer (intermediate layer)

0.25 g AgNO ₃

an AgBrI emulsion, average grain diameter 0.07 µm, 0.5 mol% AgI
1.0 g gelatin

3rd layer (low red sensitive layer)

1.7 g AgNO ₃

emulsion A1
0.82 mg RS-1
2.7 mg RS-2
0.17 mg RS-3
0.25 mg ST-11
1.5 g gelatin
0.88 g of colorless coupler C-1
0.02 g DIR coupler D-1
0.05 g colored RC-1 coupler
0.07 g colored coupler YC-1
0.75 g CPM

4th layer (highly red-sensitive layer)

2.2 g AgNO ₃

emulsion B-1
0.63 mg RS-1
2.1 mg RS-2
0.13 mg RS-3
0.32 mg ST-11
1.8 g gelatin
0.19 g of colorless coupler C-2
0.17 g CPM

5th layer (intermediate layer)

0.4 g gelatin
0.15 g white coupler W-1

6th layer (low green sensitive layer)

0.9 g AgNO ₃

emulsion A-1
1.3 mg GS-1
0.36 mg GS-2
0.26 mg GS-3
0.13 mg ST-11
1.3 g gelatin
0.54 g of colorless coupler M-1
0.24 g DIR coupler D-1
0.065 g colored coupler YM-1
0.6 g CPM

7th layer (highly green-sensitive layer)

1.25 g AgNO ₃

emulsion B-1
1.1 mg GS-1
0.3 mg GS-2
0.21 mg GS-3
0.18 mg ST-11
1.1 g gelatin
0.195 g of colorless coupler M-2
0.05 g colored coupler YM-2
0.245 g CPM

8th layer (yellow filter layer)

0.09 g of yellow colloidal silver
0.25 g gelatin
0.08 g Scavenger SC1
0.40 g formaldehyde scavenger FF-1
0.08 g CPM

9th layer (low blue-sensitive layer)

0.7 g AgNO ₃

emulsion A-1
1.3 mg BS-1
0.10 mg ST-11
2.1 g gelatin
1.1 g of colorless coupler Y-1
0.037 g DIR coupler D-1
1.14 g CPM

10th layer (highly blue-sensitive layer)

0.6 g AgNO ₃

emulsion B-1
0.68 mg BS-1
0.09 mg ST-11
0.6 g gelatin
0.2 g colorless coupler Y-1
0.003 g DIR coupler D-1
0.22 g CPM

11th layer (Mikrat layer)

0.06 g AgNO ₃

a Mikrat-Ag (Br, I) emulsion, average grain diameter 0.06 µm, 0.5 mol% iodide
1 g gelatin
0.3 g UV absorber UV-2
0.3 g CPM

12th layer (protective and hardening layer)

0.25 g gelatin
0.75 g of curing agent of the formula

so that the total layer structure had a swelling factor ≦ 3.5 after curing.

Substances used in example 1:

In the layer structures 1B to 1M, the emulsions in the layers mentioned were replaced by the emulsions listed in Table 3 in the same amount of AgNO ₃ .

Table 3

After exposing a gray wedge, the material is subjected to a color negative Processed in the "The British Journal of Photography" 1974, pages 597 and 598.

Table 4 shows the changes in the filter differences depending on the emulsions used. The filter differences (Dkop values) are the density differences between the density measured behind the blue and the behind the green filter (D _RG ), with an exposure of 0.8 log E above the sensitivity point green, which is indicated by a purple density of 0.15 is defined by veil. The specified changes occurred after the material had been stored for 14 days in a changing climate: alternately every 12 hours at 23 ° C / 95% rel. Humidity and at 32 ° C / 65% relative humidity. This climate cycle simulates the tropical climate in Malaysia.

Table 4

As storage in a tropical climate has as little impact as possible on the filters small differences in the filter differences are advantageous. This is best achieved with the materials according to the invention.

Example 2

The procedure was the same as in layer construction example 1, with the difference that that the emulsions used in the layer structures 2B to 2N with under different amounts of tellurium were matured. The deviating from the layer structure 1A Emulsions used are shown in Table 5.  

Table 5

After exposing a gray wedge, the material is subjected to a color negative Processed in the "The British Journal of Photography" 1974, pages 597 and 598.

Table 6 shows the changes in the filter differences depending on the emulsions used. The filter differences (Dkop values) are the density differences between the density measured behind the blue and the green filter (D _BG ) and between the density measured behind the red and the green filter (D _RG ), with an exposure of 0.8 log E above the sensitivity point green, which is defined by a purple density of 0.15 via fog. The specified changes occurred after the material had been stored for 14 days in a changing climate: alternately every 12 hours at 23 ° C / 95% rel. Humidity and at 32 ° C / 65% relative humidity. This climate cycle simulates the tropical climate in Malaysia.

Table 6

Example 3

The 1st to 8th layers of layer structure 3A correspond to layer structure 1A. The further layers are composed as follows:

9th layer (low blue-sensitive layer)

0.3 g AgNO ₃

emulsion A1
0.57 mg BS-1
0.044 mg ST-11
1.2 g gelatin
1.0 g of colorless coupler Y-1
0.02 g DIR coupler C-1
0.5 g CPM

10th layer (medium blue-sensitive layer)

0.5 g AgNO ₃

emulsion C1
0.76 mg BS-1
0.074 mg ST-11
0.6 g gelatin
0.3 g of colorless coupler Y-1
0.02 g DIR coupler D-1
0.3 g CPM

11th layer (highly blue-sensitive layer)

0.6 g AgNO ₃

emulsion B1
0.68 mg BS-1
0.088 mg ST-11
0.4 g gelatin
0.1 g colorless coupler Y-1
0.003 g DIR coupler D-1
0.1 g CPM

12th layer (Mikrat layer)

0.06 g AgNO ₃

a Mikrat-Ag (Br, I) emulsion with an average grain diameter of 0.06 µm, 0.5 mol% iodide
1.0 g gelatin
0.3 g UV absorber UV-2
0.3 g CPM

The 13th layer (protective and hardening layer) corresponds to the 12th layer of Layer structure 1A.

In the layer structure 3B to 3E, emulsions are used which are different quantities of selenium have been matured. Use those deviating from the layer structure 3A The emulsions are shown in Table 7.

Table 7

Table 8 shows the changes in the filter differences depending on the emulsions used. The filter differences (Dkop values) are the density differences between the density measured behind the blue and the green filter (D _BG ) and between the density measured behind the red and the green filter (D _RG ), with an exposure of 0.8 log E above the sensitivity point green, which is defined by a purple density of 0.15 via fog. The specified changes occurred after the material had been stored for 14 days in a changing climate: alternately every 12 hours at 23 ° C / 95% rel. Humidity and at 32 ° C / 65% relative humidity. This climate cycle simulates the tropical climate in Malaysia.

Table 8

As storage in a tropical climate has as little impact as possible on the filters small differences in the filter differences are advantageous. This is best achieved with the materials according to the invention.

Example 4

The procedure was exactly the same as in layer building game 3, with the difference that the emulsions used in the layer structures 4B to 4E quantities of tellurium have been matured. Use the deviating layer structure 3A The emulsions are shown in Table 9.

Table 9

Table 10 shows the changes in the filter differences depending on the emulsions used. The filter differences (Dkop values) are the density differences between the density measured behind the blue and the green filter (D _BG ) and between the density measured behind the red and the green filter (D _RG ), with an exposure of 0.8 log E above the sensitivity point green, which is defined by a purple density of 0.15 via fog. The specified changes occurred after the material had been stored for 14 days in a changing climate: alternately every 12 hours at 23 ° C / 95% rel. Humidity and at 32 ° C / 65% relative humidity. This climate cycle simulates the tropical climate in Malaysia.

Table 10

As storage in a tropical climate has as little impact as possible on the filters small differences in the filter differences are advantageous. This is best achieved with the materials according to the invention.

Claims (11)

1. Color photographic silver halide material with a support, at least two blue-sensitive, yellow coupler-containing silver halide emulsion layers, at least two green-sensitive, magenta couplers containing the silver halide emulsion layers and at least two red-sensitive, blue-green coupler-containing silver halide emulsion layers, with at least two different photosensitive silver halide genes for the same color contain a selenium and / or tellurium containing silver halide emulsion, characterized in that the amount of selenium and / or tellurium contained in the lower sensitive silver halide emulsion layer is at least 1.3 times the amount of selenium and / or tellurium in the more sensitive silver halide emulsion layer , the amount being given in moles of selenium and / or tellurium per mole of silver halide of the layers concerned. 2. Color photographic silver halide material according to claim 1, characterized ge indicates that the silver halide containing selenium and / or plates emulsions with selenium and / or tellurium compounds are chemically ripened. 3. Color photographic silver halide material according to claim 2, characterized characterized in that with at least one selenium and / or tellurium bond matured silver halide emulsions are sensitive to blue. 4. Color photographic silver halide material according to claim 2, characterized characterized in that with at least one selenium and / or tellurium bond matured silver halide emulsions are sensitive to green.   5. Color photographic silver halide material according to claim 2, characterized characterized in that with at least one selenium and / or tellurium bond matured silver halide emulsions are sensitive to red. 6. Color photographic silver halide material according to claim 1, characterized ge indicates that both contain the blue-sensitive yellow couplers Silver halide emulsion layers, as well as the green sensitive, purple coupler-containing silver halide emulsion layers with at least one Selenium and / or tellurium compound matured silver halide emulsions hold and that in the blue sensitive silver halide emulsion layers contained amount of selenium and / or tellurium compounds at least the 1,3- times the amount of selenium and / or tellurium compounds in the green sensitivity Lich silver halide emulsion layers. 7. Color photographic silver halide material according to claim 1, characterized characterized in that the selenium and / or tellurium compounds in the lower sensitive layer in an amount of 0.5 to 60 µmol / mol Silver halide of the layer in question can be used. 8. Color photographic silver halide material according to claim 2, characterized characterized in that all light-sensitive silver halide emulsions with Sulfur and gold compounds have matured. 9. Color photographic silver halide material according to claim 1, characterized characterized in that at least three photosensitive to the same color Silver halide emulsion layers with at least one selenium and / or Contain tellurium-matured silver halide emulsions, the in the low-sensitivity silver halide emulsion layer of selenium and / or tellurium compound at least 1.3 times the amount Selenium and / or tellurium compound in the medium-sensitive silver halo gene emulsion layer and that in the medium sensitive silver  amount of selenium and / or tellurium contained in the halide emulsion layer bond at least 1.3 times the amount of selenium and / or tellurium compound in the highly sensitive silver halide emulsion layer wearing. 10. Color photographic silver halide material according to claim 1, characterized characterized in that the selenium and / or tellurium-containing silver halide emulsions AgBrI or AgBrClI emulsions with ≦ 10 mol% AgI and ≦ 10 mol% are AgCl. 11. Color photographic silver halide material according to claim 10, characterized ge indicates that the silver bromide iodide containing selenium and / or tellurium or silver bromide iodide chloride emulsions to at least 70% of the project surface of tabular silver halide crystals with one aspect ratio of 5 to 30 exist.