DE19722794A1 - Colour photographic material avoiding loss of latent image stability caused by selenium or tellurium sensitiser - Google Patents

Abstract

In colour photographic silver halide (AgX) material with a base and AgX emulsion layer(s), at least one of which is sensitiser with selenium (Se) and/or tellurium (Te), the yellow filter layer between (a) the blue-sensitive layer and (b) and green- and red-sensitive layers contains compound(s) selected from 4-(4-aminobenzylidene)-5-oxo-isoxazoles of formula (I), 3-cyano-2-oxo-dihydrofurylidene-, -dihydrothiophenylidene or -pyrrolinylidene-furan or -thiophenes of formula (II) or 4-(2-acyl-2-cyanovinyl)-anilines of formula (III) as yellow filter dye. In the formulae, R<1>, R<21>, R<31> = (cyclo)alkyl, aryl or heterocyclyl; R<2>, R<3>, R<4>, R<22>, R<33>, R<34> = alkyl; or R<2>/R<3>, R<2>/R<4>, R<32>/R<33>, R<32>/R<34> = a heterocycle; R<4>, R<34> may also = hydrogen (H); X = oxygen (O), sulphur (S) or imino (NR<22>); Y = O or S; R<22> = H, (cyclo)alkyl or aryl. (I), (II) and (III) may also contain carboxyl, sulphonamido, sulphamoyl, sulphonylcarbamoyl or carbonylsulphamoyl group(s).

Description

The invention relates to a color photographic silver halide material with improved Latent image stability caused by the combination of a certain type of chemical ripening of at least one silver halide emulsion and the insert certain organic filter dyes.

It is known to incorporate light absorbing dyes in photographic materials put. Such dyes can be used, for example, in a non-light sensitive Layer can be used to underneath the photosensitive silver halo gene emulsion layers before the action of light of the absorbed by the dye Protect wavelength (filter dyes). Furthermore, it is known to use dyes Anti-halation dyes in a layer known as anti-halation layer turn. In addition, dyes can be used to improve color reproduction are used (correction dyes).

High demands are made on the dyes used for such purposes put. On the one hand, they must be suitable for the intended use have spectral absorption. Secondly, the dyes in the material are fixed without diffusing into neighboring layers. Furthermore, they should be photographically inert: in particular, the dyes must not have any adverse effects on the quality of the photographic silver halide emulsion. Furthermore the dyes, provided they are used as filter or antihalation dyes completely decolorize during processing. Corrective dyes, however should not discolor during processing and also have an excellent Long-term stability even after processing.

For example, the arylidene described in US 4,764,455 and US 4,923,788, respectively dyes of benzoylacetonitrile or 2 (5H) furanone as well as in DE 196 00 903 and EP 412 379 claimed the arylidene dyes of isoxazolone suitable spectral properties and show a satisfactory Diffusion resistance or long-term stability.  

A large number of compounds and methods have also been proposed with which the chemical ripening of silver halide emulsions is carried out is driving. The best known ripening agents are gold and sulfur compounds, e.g. B. Sodium thiosulfate as a sulfur compound. The sensitivity achieved with it it has been proposed to increase the sulfur compound entirely or partly to be replaced by selenium compounds (EP-A 661 589). Likewise, is before the sulfur compounds have been struck by certain tellurium compounds to replace.

Although according to the state of the art high quality color photographic recording materials can be manufactured, it is desirable their properties continue to improve. Sensitivity, veils, Grain, sharpness and stability of the materials called to the ever higher Requirements are made. With the introduction of the "Advanced Photographic System "with its small format these demands continue to increase. Almost Always have disadvantages in one or the other for the improvement of a property several other properties are accepted, so that such Measures are particularly valuable that allow you to make improvements without disadvantages can achieve.

This is particularly true for improvements in stability. All photographic Materials change during storage. Overlaid after exposure this process is still changing the latent image. Under extreme climates In terms of conditions, these changes are particularly rapid. Image information tion that is lost here cannot be restored during processing. Even if the known measures according to the prior art are used , the stability of the latent image is often unsatisfactory, so that measures to improve latent image stability are still being sought.

Surprisingly, it has now been found that the deterioration of the latent image stability, which occurs when at least one emulsion to increase the sensitivity is additionally selenium or tellurium-ripened, can be avoided if the between the blue-sensitive layers on the one hand and the green- and red-sensitive layers on the other hand, the yellow filter layer provided in the photographic material contains at least one compound of the general formula (I), (II) or (III) as the yellow filter dye

wherein
R ¹ , R ²¹ , R ³¹ alkyl, cycloalkyl, aryl or the residue of a heterocycle,
R ² , R ³ , R ⁴ , R ³² , R ³³ , R ³⁴ (independently of one another) alkyl or R ² and R ³ , R ² and R ⁴ , R ³² and R ³³ or R ³² and R ³⁴ together form a heterocyclic Ring,
R ⁴ and R ³⁴ also hydrogen,
XO, S, NR ²² ,
YO, S and
R ²² H, alkyl, cycloalkyl or aryl
mean, where the dyes of the formula (I), (II) or (III) optionally contain one or more carboxyl, sulfonamido, sulfamoyl, sulfonylcarbamoyl or carbonyl sulfamoyl groups.

The alkyl, cycloalkyl and aryl radicals can be substituted.

R ¹ is in particular C ₁ -C ₆ alkyl or C ₁ -C ₆ alkylsulfonylaminophenyl. R ²¹ is in particular special C ₁ -C ₆ alkylsulfonylaminophenyl or benzyl. R ³¹ is in particular phenyl or C ₁ -C ₆ alkylsulfonylaminophenyl.

R ² , R ³ , R ³² and R ³³ are in particular alkoxycarbonylalkyl radicals, R ⁴ and R ³⁴ are preferably hydrogen or methyl or R ² together with R ⁴ or R ³² together with R ³⁴ o-phenylene. X is especially O.

Examples are:

The compounds of the formulas I, II and II are preferably used in a total amount of 50 to 500 mg / m ^{2 of} photographic material.

In a preferred embodiment of the invention, at least one of the highly sensitive blue and green sensitive silver halide emulsions selenium or tellurium-ripened silver halide emulsion.

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.

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 partial 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⁻ ^5th mol / mol of silver halide and thio cyanate 10⁻ ⁷ to 10⁻ ¹ mol / mol of silver halide are used.

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

The selenium or tellurium ripening agents are preferably used in amounts of 10⁻ ⁸ to 10⁻ ⁴ mol / mol silver halide.

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 37 038, 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 37 038, 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 37 254, 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 ten metered. The emulsion was then removed to 35 ° C. within 20 minutes cools, flocculated at pH 3.5 by adding polystyrene sulfonic acid (PSS) and on finally washed at 20 ° C. The flocculate was then exposed to 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 50 ° C redispersed. 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 Ha logenide solution (1560 g ammonium bromide in 5 kg water) within 20 minutes added. After a pause of 10 minutes at 79 ° C the emulsion was brought up to 20 ° C cooled, flocculated at pH 3.5 by adding PSS and then at 20 ° C. washed. The flocculate was then filled with 4.0 kg of water and by Zu administration of 1365 g of inert gelatin and 3.5 kg of water at pH 6.5 and a tempera redispersed from 50 ° C. The center of volume of the Ag (Br, I) emulsion was 1.0 µm, the distribution width 25% and the iodide content 5.0 mol%. You get flat Chen-shaped crystals with an aspect ratio of about 4: 1.  

To prepare emulsions A1, B2 and B2, emulsions Em-A and Em-B optimally chemically ripened at 53 ° C, a pH of 6.5 and a pAg of 8.5. The amounts of ripening agent used for this are listed in Table 1.

Table 1

To prepare the emulsion B3, the emulsion Em-B was at 51 ° C, a pH of 6.3 and a pAg of 8.5 optimally chemically matured. The ones used for it Amounts of ripening agent are listed in Table 2.

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 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 A-1
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 mgRS-2
0.13 mgRS-3
0.32mg 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:

After exposure of a gray wedge, the development according to "The British Journal of Photography ", 1974, pages 597 and 598.

In the layer structures 1A to 1N, the emulsions of the 7th layer are varied; at The layered structures 1C to 1N become yellow colloidal silver in the 8th layer replaced by the dyes listed in Table 1.

Some of the materials so produced are exposed for a period of time stored for 14 days at 55 ° C and 35% relative humidity. After processing too Together with the material stored in a normal climate, this is achieved by warm storage loss of sensitivity caused determined. The results are also in the table 3 reproduced.

Table 3

As can be seen, the materials according to the invention are less susceptible to hot storage.

Claims (5)

1. Color photographic silver halide material with a support and at least one silver halide emulsion layer which contains at least one selenium and / or tellurium-ripened silver halide emulsion, characterized in that between the blue-sensitive layers on the one hand and the green and red-sensitive layers on the other hand in the photographic material provided yellow filter layer as a yellow filter dye contains at least one compound of the general formula (I), (II) or (III)
wherein
R ¹ , R ²¹ , R ³¹ alkyl, cycloalkyl, aryl or the residue of a heterocycle,
R ² , R ³ , R ⁴ , R ³² , R ³³ , R ³⁴ (independently of one another) alkyl or R ² and R ³ , R ² and R ⁴ , R ³² and R ³³ or R ³² and R ³⁴ together a hetero cyclic ring, R ⁴ and R ³⁴ also hydrogen,
XO, S, NR ²² ,
YO, S and
R ²² H, alkyl, cycloalkyl or aryl
mean, where the dyes of the formula (I), (II) or (III) optionally contain one or more carboxyl, sulfonamido, sulfamoyl, sulfonyl carbamoyl or carbonylsulfamoyl groups. 2. Color photographic silver halide material according to claim 1, characterized records that at least one of the most sensitive blue and green sensitive silver halide emulsions a selenium or tellurium-ripened silver contains halide emulsion. 3. Color photographic silver halide material according to claim 1, characterized records that the selenium and / or tellurium-ripened silver halide emulsion 2 to Contains 12 mol% AgI, 80 to 98 mol% AgBr and 0 to 18 mol% AgCl. 4. Color photographic silver halide material according to claim 1, characterized in that the compound of formula I, II and III are used in a total amount of 50 to 500 mg / m ² . 5. Color photographic silver halide material according to claim 1, characterized in that the selenium or tellurium ripening agents are used in an amount of 10⁻ ⁸ to 10⁻ ⁴ mol / mol silver halide.