DE19920354A1 - Color photographic silver halide material, e.g. negative, reversal or positive film or color or color reversal paper, with sulfur and selenium and/or tellurium sensitizers is stabilized with acid hexahydro-s-triazine-2-thione - Google Patents

Abstract

In color photographic silver halide (AgX) material with a base and light-sensitive AgX emulsion layer(s) in which the emulsion is sensitized with compounds giving (a) sulfur and (b) selenium and/or tellurium, the emulsion is stabilized with an acid hexahydro-s-triazine-2-thione (I). In color photographic silver halide (AgX) material with a base and light-sensitive AgX emulsion layer(s) in which the emulsion is sensitized with compounds giving (a) sulfur and (b) selenium and/or tellurium, the emulsion is stabilized with an acid hexahydro-s-triazine-2-thione of formula (I). A = an acid group; R = a 1-5 carbon (C) aliphatic bridge; R1 = hydrogen (H) or 1-4 C alkyl; and R2, R3 = H or methyl.

Description

The invention relates to a color photographic recording material with color sensitivity lized silver halide layers, which has increased sensitivity. In particular The invention also relates to a color photographic recording or copying material, which has increased sensitivity in that at least one of the used spectrally sensitized light-sensitive silver halide emulsions with a Selenium compound matured and with a hexahydro-s-triazine-2-thione compound, resp. a salt thereof, is stabilized.

It is known that spectrally sensitized emulsions produce high sensitivity Can be ripened by in addition to the so-called chemical ripening Sulfur-releasing compounds also selenium or tellurium-releasing compounds genes can be applied to the surface of the silver halide crystals that are capable are to build riding centers and / or sensitivity centers. Besides that, you can some of these connections also intercept defect electrons and the defektelek Suppress tron-induced desensitization.

However, it is known that in the chemical ripening with selenium or tellurium bonds often emulsions with high sensitivity, but also with flat gradation arise, and that the ripening with selenium or tellurium compounds in many cases associated with an increase in the veil. This leads to emulsions prepared in this way for certain highly sensitive color photographic materials materials become unusable.

It is also known that certain stabilizers from the ranks of the mercaptotetra zoles, the mercaptothiadiazoles and the 3-mercapto-1,2,4-triazoles are suitable the fog-producing effect of selenium compounds in chemical chemistry to counteract fungus. Simple mercaptoazoles are also used as stabilizers for Selenium or tellurium ripening described.

However, some of the sensitivity gained is then lost again.

It was surprisingly found that hexahydro-s-triazine-2-thione, which is an acidic Group wear, are eminently suited to the haze-producing Effect of selenium or tellurium compounds in chemical ripening and afterwards counteract this without affecting the sensitivity gained for the stabilization effect must be sacrificed. In addition, when using the erfindungsge moderate hexahydro-s-triazine-2-thione compounds to highly sensitive silver chlorine rid, silver bromide or silver bromide iodide emulsions in highly sensitive materials In addition to increased sensitivity, taking materials also has an improved hold The availability of the spectral sensitization can be determined, with the spectral sensitivity bilized sensitivity does not decrease on storage and the color separation and the developability of the latent image is not impaired.

Chemical ripening is preferred with the participation of gold (I) compounds, z. B. in the form of gold (I) thiocyanate complexes carried out.

The acidic hexahydro-s-triazine-2-thiones according to the invention are, for. B. as pale known accelerating additives to bleach or bleach-fix baths. It is also known that they show a silver-fixing effect in higher concentrations. she are preferably hydrophilic. You can choose to be sensitized or already sensitized ized emulsion at some point between the precipitation of the emulsion and their introduction into the casting approach in the form of an aqueous solution who added the, so either separated in time before the addition of the dyes or together with the sensitizing dyes. Other sequences of addition are also possible.

The invention thus provides a color photographic silver halide material with a support and at least one light-sensitive silver halide emulsion layer, the silver halide emulsion of which is matured with (a) sulfur-donating and (b) selenium and / or tellurium-donating compounds, characterized in that the silver halide emulsion with a compound of Formula (I) is stabilized

wherein
A an acidic group,
R is an aliphatic bridge member with 1 to 5 carbon atoms,
R ₁ H or an alkyl group with 1 to 4 carbon atoms and
R ₂ and R ₃ independently of one another denote H or CH ₃ .

A is preferably a carboxylic acid, sulfonic acid, phosphonic acid, phosphoric acid, acylsulfonamide, acylurea or sulfonylurea group bonded via O, but particularly preferably a carboxyl group.
R is preferably a straight-chain or branched, optionally substituted alkylene group, but in particular an unsubstituted C ₁ -C ₄ alkylene group.

Suitable examples are listed below:

Possible selenium and tellurium ripening agents are:

• - heterocyclic selenones or tellurons, especially selenones,
• - tri- or tetrasubstituted or cyclic selenium or telluroureas;
• - Phosphine selenides or tellurides with three ligands that have carbon or O or N are connected as heteroatoms with the phosphorus atom, in particular their triarylphosphine selenides;
• - Diaryldiselenide or Diarylditelluride;
• - aryl selenoamides;
• - isoselenazolones;
• - aryl selenocyanates with a polar group;
• - cyclic telluroethers with a 5-8 membered ring;
• - transition metal-organic tellurides.

Suitable selenium and tellurium ripening agents are listed below

The compounds of the formula (I) are used in particular in an amount of 10 ^-9 to 10 ^-3 mol / mol of silver halide, preferably 10 ^-6 to 10 ^-4 mol / mol of silver halide.

Spectral sensitizing dyes that can be used with advantage in the presence of the fiction according to acidic hexahydro-s-triazine-2-thione compounds can be used can be found in all common sensitizer classes, but preferably in the series of monomethine, trimethine and pentamethine cyanine dyes. At Games for these dyes are in Th. James, The Theory of the Photography Process, 3rd Edition (Macmillan 1966), pp. 198-228.

The dyes can be silver halide for the entire range of the visible Sensitize the spectrum and also for the infrared range. Particularly preferred dyes are the mono-, tri- and pentamethine cyanines of Benzoxazole, benzimidazole, benzthiazole, naphthoxazole, naphthiazole or Benzoselenazole series, each of which has further substituents or in the benzene rings carry further rings or ring systems as substituents or in fused form can, among the pentamethine cyanines, continue to have those whose methine part was present is part of a partially unsaturated ring. The dyes can be cationic, in Form of betaines or sulfobetaines can be uncharged or anionic.

The chemical ripening can with particular advantages in the presence of the fiction according to acidic hexahydro-s-triazine-2-thione compounds and the sensitization tion dyes are carried out. The preferred amounts of color used substances are generally not changed.

The silver halide used can be selected from silver chloride, silver bromide, silver chloride bromide in freely selectable composition, silver bromide iodide and silver bromide chloride-iodide, there can also be epitaxial growth forms of Sil Berchloride on silver iodide or from silver iodide on silver chloride or silver bro have midchlorid, the crystals can be homogeneous or zone-shaped be inhomogeneous, there can be single crystals or, single or multiple be twinned crystals. The emulsions can consist of predominantly compact, predominantly rod-shaped or predominantly leaf-shaped crystals exist, they can also contain epitaxial growths. In the case of leaflets shaped crystals, those with an aspect ratio above 3: 1 are preferred, those with an adjacent edge ratio close to 1 are particularly preferred.

The emulsion crystals can also be doped with certain foreign ions, the affect the shape of the gradation or the Schwarzschild effect, or the stability improve the latent image, especially with complex-bound polyvalent ones Transition metal cations, for example with hexacyanoferrate (II) ions, hexacya noruthenate (II) ions or with precious metal cations that are trivalent and one have octahedral ligand environment, for example with ruthenium (III) -, Rhodium (III), osmium (III) or iridium (III) salts, with the function of Foreign ion doping essentially goes beyond that of a pure lattice disruption and aims at the installation of so-called shallow electron traps.

The emulsions can be designed largely homodisperse or heterodisperse, they can accordingly by conventional precipitation, by one to more double enema or with the micratum solution method the. It can also be what are known as converting emulsions.

The emulsions can also be sensitized with reducing ripening agents. The reduction ripening can also occur in the course of the precipitation of the emulsion crystals in the Depth of the crystal can be built up, with the reduction nuclei in the further Growth of the crystals are covered. As a reducing ripening agent, two can 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 can be used. Organically soluble, rapidly and completely adsorbable on the silver halide tion ripening agents are preferred.

The stabilization of spectrally sensitized emulsions containing sulfur, selenium and Gold is ripened by the compounds of formula (I) in combination with the long-term stabilization of color photographic materials by palladium (II) ver ties are particularly important.

Examples of color photographic materials are color negative films, color reversal films, Color positive film, color photographic paper and color reversal photographic paper. An overview can be found in Research Disclosure 37038 (1995) and Research Disclosure 38957 (1996).

The photographic materials consist of a support on which at least one light-sensitive silver halide emulsion layer is applied. As a carrier own Thin films and foils are particularly suitable. An overview of carrier materials lien and auxiliary layers applied to their front and back is in Research Disclosure 37254, Part 1 (1995), p. 285 and in Research Disclosure 38957, Part XV (1996), p. 627.

The color photographic materials usually contain at least one red each sensitive, green sensitive and blue sensitive silver halide emulsions layer and optionally intermediate layers and protective layers.

Depending on the type of photographic material, these layers can be different be arranged. This is shown for the most important products:

Color photographic films such as color negative films and color reversal films have the following sequence on the carrier 2 or 3 red-sensitive, blue-green 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 tral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers usually being closer to the wearer are ordered than the more sensitive sub-layers.

Between the green-sensitive and blue-sensitive layers is usually A yellow filter layer is attached to prevent blue light from penetrating the underneath lowing layers.

The possibilities of the different layer arrangements and their effects on the photographic properties are in J. Inf. Rec. Mats., 1994, Vol. 22, Pp. 183-193 and Research Disclosure 38957 Part XI (1996), p. 624 ben.

Color photographic paper, which is generally much less sensitive to light as a color photographic film, exhibits in the order given below usually a blue-sensitive, yellow-coupling silver halide on each support nide emulsion layer, a green sensitive, purple coupling silver halide emulsion sion layer and a red-sensitive, blue-green coupling silver halide module sion layer on; the yellow filter layer can be omitted.

There may be deviations in the number and arrangement of the light-sensitive layers to achieve certain results. For example can all highly sensitive layers in a layer package and all low-sensitivity These layers combine to form another layer package in a photographic film be set in order to increase the sensitivity (DE-25 30 645).

The 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 and in Research Disclosure 38957, Part II.A (1996), p. 598.

Information on suitable silver halide emulsions, their production, ripening, Sta bilization and spectral sensitization including appropriate spectral sensitization Sators can be found in Research Disclosure 37254, Part 3 (1995), p. 286, in Research Disclosure 37038, part XV (1995), p. 89 and in Research Disclosure 38957, part V.A (1996), p. 603.

Photographic materials with camera sensitivity usually contain Sil berbromidiodide emulsions, which may also contain small amounts of silver chloride may contain. Photographic copy materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288, in Research Disclosure 37038, Part II (1995), p. 80 and in Research Disclosure 38957, Part X.B (1996), p. 616. The maximum absorption of the dyes formed from the couplers and the color developer oxidation product is preferably in the following ranges: yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 to 700 nm.

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

Information on such compounds, especially couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290, in Research Disclosure 37038, Part XIV (1995), p. 86 and in Research Disclosure 38957, Part X.C (1996), p. 618.

The mostly hydrophobic color couplers, but also other hydrophobic components of the Layers are commonly used in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in a aqueous binder solution (usually gelatin solution) emulsified and lie after drying the layers as fine droplets (0.05 to 0.8 µm diam ser) in the layers.

Suitable high-boiling organic solvents, methods of incorporation into the Layers of a photographic material and other methods, chemical connection Applications to introduce into photographic layers can be found in Research Disclosure 37254, part 6 (1995), p. 292.

The usually applied between layers of different spectral sensitivity Ordered non-photosensitive interlayers may contain agents that unwanted diffusion of developer oxidation products from a light temp sensitive to another light-sensitive layer with different spectral Prevent sensitization.

Suitable compounds (white couplers, scavengers or EOP catchers) can be found in Research Disclosure 37254, Part 7 (1995), p. 292, in Research Disclosure 37038, Part III (1995), p. 84 and in Research Disclosure 38957, Part X.D (1996), p. 621 ff.

The photographic material can also contain UV light absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _Min dyes, plasticizers (latices), biocides and additives to improve the coupler and dye stability and to reduce color fog and to reduce yellowing and others. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292, in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff and in Research Disclosure 38957, Parts VI, VIII, IX and X (1996), pp. 607 and 610 ff.

The layers of color photographic materials are usually hardened; h., that binder used, preferably gelatin, is made by suitable chemical Networked processes.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), P. 294, in Research Disclosure 37038, Part XII (1995), p. 86 and in Research Disclosure 38957, Part II.B (1996), p. 599.

After imagewise exposure, color photographic materials develop their character processed according to different procedures. Details on the Ver Driving practices and the chemicals required for them are in Research Disclosure 37254, Part 10 (1995), p. 294, in Research Disclosure 37038, Parts XVI to XXIII (1995), p. 95 ff and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), p. 630 ff published along with exemplary materials.

Examples example 1 Highly sensitive emulsion with tabular crystals (all data in µmol additive refer to 1 mol AgNO ₃ ) Example 1.1. (Comparison)

A silver bromide-iodide emulsion with an average grain diameter of 1.5 μm, corresponding to the average diameter of the circle of equal area, an aspect ratio of 7.5 and an average iodide content of 9 mol%, based on total silver, is obtained with
Tetrachloroauric acid (2 µmol),
Potassium thiocyanate (250 µmol),
Sodium thiosulphate (6 µmol),
Triphenylphosphine selenide (4 µmol) and
2-mercaptobenzothiazole (100 µmol) (stabilizer not according to the invention)
Matured to the optimum sensitivity.

Example 1.2. (Comparison)

Example 1.1. is repeated, but with the difference that the not fiction appropriate stabilizer 2-mercaptobenzothiazole (100 µmol) added after ripening will practice.

Example 1.3. (Invention)

Example 1.1. is repeated, but with the difference that instead of the 2- Mercaptobenzthiazoles RST-1 (100 µmol) is used.

Example 1.4. (Invention)

Example 1.3. is repeated, but with the difference that the erfindungsge The correct RST-1 ripening stabilizer is only added after ripening has ended.

Example 1.5. (Comparison)

Example 1.1. is repeated, but with the difference that the following ripening agent is used instead of the named ripening agent composition:
Tetrachloroauric acid (2 µmol),
Potassium thiocyanate (250 µmol),
Sodium thiosulphate (6 µmol),
Trispyrrolidinophosphate telluride (4 µmol) and
2-mercaptobenzothiazole (100 µmoles); (stabilizer not according to the invention).

Example 1.6. (Comparison)

Example 1.5. is repeated, but with the difference that the not fiction appropriate ripening stabilizer 2-mercaptobenzothiazole added only after ripening has ended will give.

Example 1.7. (Invention)

Example 1.5. is repeated, but with the difference that instead of the 2-mercaptobenzothiazoles RST-2 (100 µmol) is used.

Example 1.8. (Invention)

Example 1.6. is repeated, but with the difference that the erfindungsge appropriate ripening stabilizer RST-2 is added after ripening has ended.

Example 1.9. (Invention)

Example 1.1. is repeated, but with the difference that the following ripening agent is used instead of the named ripening agent composition:
Tetrachloroauric acid (2 µmol),
Potassium thiocyanate (250 µmol),
Sodium thiosulphate (6 µmol),
N-methylbenzothiazole selenone-2 (4 µmol) and
inventive stabilizer RST-6 (100 μmol).

Example 1.10. (Invention)

Example 1.9. is repeated, but with the difference that the erfindungsge The correct RST-6 ripening stabilizer is only added after ripening has ended.

Manufacture of photographic layers

The emulsions are stabilized with 100 μmol hydroxymethyl-tetraazaindene and, after the addition of a color coupler emulsified, are applied with the following amounts (in g per m ² ) to a 120 μm thick substituted cellulose triacetate carrier.

Cyan Coupler C-1 0.3 Tricresyl phosphate 0.45 gelatin 0.7 Emulsions of Examples 1.1 to 1.10 (each g AgNO ₃ ) 0.85

The individual tracks were coated with a protective layer of the following composition and hardened:

Hardener H-1 0.02 gelatin 0.01

The individual samples were processed further immediately after casting. They were exposed to daylight behind a graduated gray wedge and then processed according to the process described in "The British Journal of Photography" 1974, p. 597. The sensitivities were determined after densitometric measurements at a density of 0.2 over D _min in relative ISO units. The sensitivity of experiment 1.1. was set as 100.

The results are shown in the table below:

The blocks used have the following formulas:

Example 2 Emulsions Em-2/1 to 2/7

The following solutions are used:

Solution 1:
7000 ml deionized water
600 g gelatin
1.0 g of 1- (3,6-dithiaoctyl) urea

Solution 2:
7000 ml deionized water
1300 g sodium chloride

Solution 3:
7000 ml deionized water
3000 g of silver nitrate

Emulsion 2.1.

Solutions 2 and 3 are in the course of 120 minutes at 60 ° C and at a pAg of 7.7 added simultaneously to solution 1 with vigorous stirring. It will be a Silver chloride emulsion with an average particle diameter of 0.90 µm was obtained th. The ratio of gelatin to silver is 0.18. The emulsion is made with Polysty rolsulfonic acid flocculated, washed and redispersed with enough gelatin that the Gelatin / silver ratio is 0.56. The emulsion contains 1 mole of silver chloride per kg.

Subsequently, optimal ripening takes place at a pH of 4.5 with 3.5 µmol KAuCl ₄ and 1.5 µmol Na ₂ S ₂ O ₃ per mol Ag at 60 ° C.

After chemical ripening, the emulsion becomes with 300 µmol of the blue sensitisa tors BS-1 spectrally sensitized and with 280 µmol 1- (3-acetaminophenyl) -5-mer captotetrazole stabilized.

Emulsion 2.2.

Different from Emulsion 2.1. in that during ripening the amount of KAuCl _{4 is} reduced to 1.5 μmol and the amount of Na ₂ S ₂ O _{3 is} reduced to 0.5 μmol per mol of Ag and an additional 2.0 μmol of the selenium ripening agent Se-14 is used will.

Emulsion 2.3.

Different from Emulsion 2.1. in that the amount of KAuCl _{4 is} reduced to 1.5 μmol and the amount of Na ₂ S ₂ O ₃ to 0.5 μmol per mol of Ag during ripening and an additional 2.0 μmol of the selenium ripening agent Se-14 and 200 μmol of the frost stabilizer RST-3 according to the invention can be used.

Emulsions 2.4. until 2.7.

Different from 2.2. in that during ripening about 2.0 µmol of selenium ripening agent Se-14 additionally 200 μmol of the ripening stabilizers according to the invention RST-4, RST-9 and RST-14 can be used.

The sensitized and stabilized emulsions 2.1 to 2.7 are each the Emulsified of the yellow coupler GB-1 in tricresyl phosphate and added to one of the two on one side coated with polyethylene coated paper substrate.

The cast individual layers contain per m ²
0.63 g AgNO ₃ ,
1.38 g gelatin,
0.95 g yellow coupler GB-1
0.29 g tricresyl phosphate.

The material is hardened by applying a protective layer of 0.2 g gelatin and 0.3 g hardening agent H-1 per m ^2. Samples of it are exposed imagewise behind a gradient wedge and processed according to the Ektacolor RA-4 process.

The blocks used have the following formulas:

The sensitometric results are shown in Table 1:

From the results, it can be seen that high sensitivity with low Veil only with the inventive combination of one according to the invention Selenium ripening agent and a polar ripening stabilizer according to the invention can be achieved.

When using a frost stabilizer not according to the invention, however, to obtain high minimum densities.

Claims (5)

1. Color photographic silver halide material with a support and at least one light-sensitive silver halide emulsion layer, the silver halide emulsion of which is matured with (a) sulfur-releasing and (b) selenium and / or tellurium-releasing compounds, characterized in that the silver halide emulsion with a compound of the formula (I ) is stabilized
wherein
A an acidic group,
R is an aliphatic bridge member with 1 to 5 carbon atoms,
R ₁ H or an alkyl group with 1 to 4 carbon atoms and
R ₂ and R ₃ independently of one another denote H or CH ₃ . 2. Color photographic silver halide material according to claim 1, characterized characterized in that A is a carboxylic acid, sulfonic acid, phosphonic acid, over O bound phosphoric acid, acylsulfonamide, acylurea or Is sulfonylurea group. 3. Color photographic silver halide material according to claim 1, characterized in that A is a carboxyl group and R is a C ₁ -C ₄ alkylene group. 4. Color photographic silver halide material according to claim 1, characterized in that the compound of the formula (I) is used in an amount of 10 ^-9 to 10 ^-3 mol / mol of silver halide. 5. Color photographic silver halide material according to claim 1, characterized in that the compound releasing selenium and / or tellurium is selected from the following classes:

• - heterocyclic selenones or tellurons;
• - Tri- or tetrasubstituted or cyclic selenium or tellurourea substances;
• - Phosphine selenides or tellurides with three ligands that are verbun via carbon or O or N as heteroatoms with the phosphorus atom;
• - Diaryldiselenide or Diarylditelluride;
• - aryl selenoamides;
• - isoselenazolones;
• - aryl selenocyanates with a polar group;
• - cyclic telluroethers with a 5-8 membered ring;
• - transition metal-organic tellurides.