DE19902959A1 - Color photographic material, especially color negative film, contains selenium and/or tellurium in red-sensitive emulsion and smaller amount in at least one emulsion of different 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 different spectral sensitivity contain selenium (Se) and/or tellurium (Te).

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 differently spectrally sensitized, light-sensitive silver halide emulsion layers one ripened with at least one selenium or tellurium compound Contain silver halide emulsion, which is characterized in that the filter hardly change differences during storage under tropical conditions.

It is known that spectrally sensitized emulsions are too sensitive can be ripened by in addition to sw releasing compounds also selenium or tellurium releasing compounds applied the surface of the silver halide crystals or selenium or tellurium giving compounds are incorporated into the silver halide crystals.

From DE 197 19 841 it is known that there is a good sensitivity ratio obtains storage stability if the blue sensitive, containing yellow coupler Layer contains more selenium and tellurium than the red or green sensitive, teal or layers containing magenta couplers.

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-untrue 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 one red sensitivity Liche, cyan coupler layer and at least one blue or green sensitive layer containing yellow or purple couplers a selenium and / or Contains tellurium containing silver halide emulsion and those in the red sensitive Silver halide emulsion layers contain amount of selenium and / or tellurium at least 1.3 times the amount of selenium and / or tellurium in the blue or green sensitive silver halide emulsion layers, the amount in mol Selenium and / or tellurium per mole of silver halide of the layers concerned give is. The amount is preferably 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; Arylselenocyanate with a polar group and cyclic telluro ether 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 the 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 of silver halide and 10 ^-7 to 10 ^-1 mol / mol of 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 Emulsions can take place 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 is in Research Disclosure 37254, Part 1 (1995), P. 285.

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 are usually closer to the carrier are classified as 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 pro Dyes formed in the product 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 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 an aq emulsified with a binder solution (usually gelatin solution) drying the layers as fine droplets (0.05 to 0.8 µm diameter) in before the layers.

Suitable high-boiling organic solvents, methods for incorporation into the Layers of photographic material and other methods, chemical ver Finding bonds in 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), 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 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 20 Minutes dosed. After a pause of 10 minutes at 79 ° C, the emulsion cooled to 20 ° C, flocculated at pH 3.5 by adding PSS and then at Washed at 20 ° C. The flocculate was then filled up with 4.0 kg of water and by adding 1365 g of inert gelatin and 3.5 kg of water at pH 6.5 and one Temperature of 50 ° C redispersed. The center of volume of the Ag (Br, I) emul ion was 1.0 µm, the distribution width was 25% and the iodide content was 5.0 mol%. Man receives platelet-shaped crystals with an aspect ratio of approximately 4: 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 1

To prepare the emulsions Em A3 and Em B5 to Em B7, the Emulsions Em A and Em B at 51 ° C, a pH of 6.3 and a pAg of 8.5 optimally chemically matured. The amounts of ripening agent used for this are shown in Table 2 listed, tetrachloroauric acid was used as the gold compound.

Table 2

The selenium and tellurium compounds have the following formulas:

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 cellulose triacetate support. 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 1N, the emulsions in the layers mentioned were replaced by the emulsions specified 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 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% rel. Humidity. This climate cycle simulates the tropical climate in Malaysia.

Table 4

Since storage in a tropical climate has no influence on the Should have filter differences, small changes in the filter differences are advantageous arrested. This is best achieved with the materials according to the invention.

Layer structure 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 also differ quantities of tellurium have been matured. The different from the layer structure 1A ver Emulsions used are shown in Table 5.  

Table 5

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 / 63% rel. Humidity. This climate cycle simulates the tropical climate in Malaysia.

Table 6

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 (10)

1. Color photographic silver halide material with a support, at least two blue-sensitive, silver coupler-containing silver halide emulsion layers, at least two green-sensitive, magenta coupler containing the silver halide emulsion layers and at least two red-sensitive, cyan-coupler-containing silver halide emulsion layers, at least two differently spectrally and / or silver-sensitized / silver halide light-sensitive selulsions Have tellurium-containing silver halide emulsion, characterized in that at least one red-sensitive layer containing cyan couplers and at least one blue- or green-sensitive layer containing yellow or purple couplers contains a selenium and / or tellurium-containing silver halide emulsion and contains the emulsion layers in the red-sensitive silver halide Amount of selenium and / or tellurium at least 1.3 times the amount of selenium and / or tel lur in the blue or green sensitive silver halide emulsion layers, the amount being given in moles of selenium and / or tellurium per mole of silver halide of the layers in question. 2. Color photographic silver halide material according to claim 1, characterized ge indicates that the silver halide containing selenium and / or tellurium emulsions with selenium and / or tellurium compounds were ripened. 3. Color photographic silver halide material according to claim 2, characterized ge indicates that the most sensitive, red-sensitive silver halide emulsion layer with at least one selenium and / or tellurium compound contains ripened silver halide emulsion. 4. Color photographic silver halide material according to claim 2, characterized ge indicates a green sensitive silver halide emulsion layer  a silver ripened with at least one selenium and / or tellurium compound contains halide emulsion. 5. Color photographic silver halide material according to claim 4, characterized ge indicates that the highly sensitive, green-sensitive silver halo gene emulsion layer one with at least one selenium and / or tellurium contains bonded matured silver halide emulsion. 6. Color photographic silver halide material according to claim 1, characterized ge indicates that containing at least one blue-sensitive yellow coupler Silver halide emulsion layer, at least one green sensitive, purple coupler-containing silver halide emulsion layer and at least one red sensitive silver halide emulsion layer containing cyan couplers a silver ripened with at least one selenium and / or tellurium compound contains halide emulsion and that in the red sensitive silver halide amount of selenium and / or tellurium compounds contained in the emulsion layers 1.3 times the amount of selenium and / or tellurium compounds in the green sensitive silver halide emulsion layers and those in the green sensitive silver halide emulsion layers Selenium and / or tellurium compounds, 1.3 times the amount of selenium and / or tellurium compounds in the blue sensitive silver halide is emulsion layers. 7. Color photographic silver halide material according to claim 1, characterized ge indicates that the selenium and / or tellurium compounds in an amount from 0.5 to 30 µmol / mol silver halide of the layer in question become. 8. Color photographic silver halide material according to claim 2, characterized ge indicates 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 ge indicates that the silver halide containing selenium and / or tellurium Emulsions AgBrI or AgBrClI emulsions with ≦ 10 mol% AgI and ≦ Are 10 mol% AgCl. 10. Color photographic silver halide material according to claim 9, 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 an aspect ratio ratio of 5 to 30 exist.