DE19719841A1 - Colour photographic silver halide material with increased ratio of fresh speed to storage stability - Google Patents

Abstract

Colour photographic silver halide (AgX) material has a base and blue-, green- and red-sensitive AgX emulsion units containing yellow, magenta and cyan couplers respectively, each with >= 2 AgX emulsion layers. At least 2 AgX emulsion layers of different colour sensitivity contain selenium (Se) and/or tellurium (Te) compounds. The novelty is that at least one blue-sensitive emulsion layer contains >= 1.3 times as much Se and/or Te as the green- or red-sensitive emulsion layer (based on mole Se and/or Te per 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 differently spectrally sensitized, light-sensitive silver halide emulsion layers with at least one selenium or tellurium compound matured silver contain halide emulsion, which is characterized by an improved sensitivity at no high storage veil.

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-releasing verbin applied to the surface of the silver halide crystals or selenium or Tellurium-releasing compounds built into the silver halide crystals will.

It is also known that in chemical ripening with selenium or tellurium compounds increasing sensitivity is often an undesirable Raises the bearing curtain.

The object of the invention was therefore to develop a material whose sensitivity is improved in the fresh state without the sensitivity during storage sensitivity or an unchanged sensitivity at low Loss of sensitivity during storage shows. This applies to normal bearings conditions under extreme climatic conditions such as warm or humid storage.

The task is therefore to provide a material with a better ratio of Fresh sensitivity to storage stability.  

The object is achieved in that at least one is blue sensitive layer containing yellow couplers and at least one red or green sensitive layer containing cyan or magenta couplers a selenium and / or Contains tellurium containing silver halide emulsion and those in the blue 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 green or red-sensitive silver halide emulsion layers, the amount in mol Selenium and / or tellurium per mole of silver halide of the layers in question 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; isoselenazolone; 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 are:

The carbocyclic 5-rings of the substances Se-79, Se-81, Se-82, Se-83, Se-85, Se-87, Te-25, Te-32, Te-34, Te-37, Te-38, Te-40, Te-42, Te-45, Te-46, Te-47 Cyclopentadienyl anion substituent.  

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 on thio eyanate 10⁻ ⁷ to 10⁻ ¹ mol / mol silver halide 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

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 moles per mole of silver.

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

Spectral sensitizing dyes are in all common classes of sensitizers to be found, 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 described.

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, Naphthoxazole, naphththiazole or benzoselenazole series, each in the Benzene rings carry further substituents or further rings or ring systems as Can carry substituents or in fused form, among the pentamethine Cyanines, in turn, are those whose methine part is part of a partially unused saturated ring. The dyes can be cationic, in the form of betaines or Sulfobetaines uncharged, or 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 preferably added after 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 bromide in freely selectable composition, silver bromide iodide as well Silver bromide chloride iodide exist, it can also be epitaxial Forms of growth of silver chloride on silver iodide or of silver iodide on silver act chloride or silver bromide chloride, the crystals can be homogeneous in itself or be inhomogeneous in zones, it can be simple crystals, simple or multiple twinned crystals. The emulsions can predominantly compact, predominantly rod-shaped or predominantly platelet-shaped Crystals exist, they can also contain epitaxial growths. In the case platelet-shaped crystals are those with an aspect ratio above 3: 1 preferred, those with a neighboring edge ratio close to 1 are 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, hexadcyanoruthenate (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 will. 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 precipitation of the emulsion crystals in the Depth of the crystal are built up, with the reduction ripening seeds in the white growth of the crystals are covered. As a reducing ripening agent divalent tin compounds, phosphane tellurides, N-arylhydrazides, salts of Formamidine-C-sulfinic acid, boranates or other complex hydrides, but also macrocyclic polyamines and metal complexes made from them, with advantage be used. Organically soluble, quickly and completely on silver halide adsorbable 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 the 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 Auxiliary layers applied on the back is in Research Disclosure 37 254, Part 1 (1995), p. 285.

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 liche, yellow-coupling silver halide emulsion layers. The layers same spectral sensitivity differ in their photographic emp 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 more common a yellow filter layer, which prevents blue light from entering the to get layers below.

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 to another layer package in a photographic film be summarized 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 37 254, part 2 (1995), p. 286.

Information about suitable silver halide emulsions, their preparation, maturation, Stabilization and spectral sensitization including suitable spectrals sensitizers can be found in Research Disclosure 37 254, Part 3 (1995), p. 286 and in Research Disclosure 37 038, 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 emuls ions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37 254, Part 4 (1995), p. 288 and in Research Disclosure 37 038, Part II (1995), p. 80. The maximum absorption of that from the couplers and the color developer oxide dyes formed product is 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 Reaction with the developer oxidation product release compounds, the photo are graphically effective, e.g. B. DIR couplers that have a development inhibitor columns.  

Information on such connections, in particular couplers, can be found in Research Disclosure 37 254, 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 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 through knife) in the layers.

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 37 254, 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 37 254, 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 and to reduce the color fog, plasticizers (latices). , Biocide and others included.

Suitable compounds can be found in Research Disclosure 37 254, Part 8 (1995), P. 292 and in Research Disclosure 37 038, parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff.

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

Suitable hardener substances can be found in Research Disclosure 37 254, Part 9 (1995), p. 294 and in Research Disclosure 37 038, Part XII (1995), page 86.

After imagewise exposure, color photographic materials become their character ter 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 37 038, Parts XVI to XXIII (1995), p. 95 ff. Published 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 with 4.0 kg of water and through Add 1365 g of inert gelatin and 3.5 kg of water at pH 6.5 and one Temperature of 50 ° C redispersed. The volume focus of 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 approximately 4: 1 are obtained.  

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

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 of} 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 of 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 of 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 of 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 of 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 of 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 of 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 of} 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 given 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 relative fresh sensitivities (at density 0.2 above fog) of the layer structures and the relative loss of sensitivity related to the Material without selenium after storage for 14 days at 60 ° C and 35% relative humidity specified.

Table 4

As can be seen, the materials according to the invention have an improved ratio from fresh sensitivity to warm storage stability.  

Layer structure example 2

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

Table 5

Table 6 shows the relative fresh sensitivities (at density 0.2 above fog) of the layer structures and the relative loss of sensitivity related to the Material without tellurium after storage for 14 days at 60 ° C and 35% relative humidity specified.

Table 6

As can be seen, the materials according to the invention also show a tellurium ripening significantly improved ratio of fresh sensitivity to warm storage stability.

Claims (10)

1. Color photographic silver halide material with a support, at least two blue-sensitive silver halide emulsion layers containing yellow couplers, at least two green-sensitive silver halide emulsion layers containing magenta couplers and at least two red-sensitive silver-halide emulsion layers containing cyan couplers, at least two differently spectrally sensitized tellurium silver halide or at least one photosensitive silver halide or halide emulsion , characterized in that at least one blue-sensitive layer containing yellow couplers and at least one red- or green-sensitive layer containing cyan or magenta couplers contains a silver halide emulsion containing selenium and / or tellurium and the amount of selenium and / or ion-containing layers contained in the blue-sensitive silver halide emulsion layers or tellurium at least 1.3 times the amount of selenium and / or tellu r in the green or red-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 characterized in that the selenium and / or tellurium containing silver halide emulsions with selenium and / or tellurium compounds were ripened. 3. Color photographic silver halide material according to claim 2, characterized records that the highly sensitive, blue-sensitive silver halide emul ion 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 records that a green-sensitive silver halide emulsion layer with a  at least one selenium and / or tellurium compound matured silver halide contains emulsion. 5. Color photographic silver halide material according to claim 4, characterized records that the highly sensitive, green sensitive silver halide emul ion layer with at least one selenium and / or tellurium compound contains ripened silver halide emulsion. 6. Color photographic silver halide material according to claim 1, characterized records 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 blue 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 containing amount of selenium and / or Tellurium compounds, 1.3 times the amount of selenium and / or Tellurium compounds in the red sensitive silver halide emulsions is stratification. 7. Color photographic silver halide material according to claim 1, characterized records that the selenium and / or tellurium compounds in an amount of 0.5 up to 30 µmol / mol silver halide of the layer in question. 8. Color photographic silver halide material according to claim 2, characterized records that all photosensitive silver halide emulsions with sulfur and Gold compounds have matured.   9. Color photographic silver halide material according to claim 1, characterized characterized in that the silver halo containing selenium and / or tellurium genide emulsions AgBrI or AgBrClI emulsions with ≦ 10 mol% AgI and ≦ 10 mol% of AgCl. 10. Color photographic silver halide material according to claim 9, characterized characterized in that the selenium and / or tellurium containing silver bromide iodide 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.