DD265474A1 - PHOTOGRAPHIC SILVER HALOGENIDE EMULSION - Google Patents

Abstract

The invention relates to a photographic silver halide emulsion for the production of photographic materials. The aim and object of the invention are to provide emulsion with improved sensitivity, low minimum density and good durability. The object is achieved according to the invention in a photographic emulsion with gold compounds, the gold compounds of the general formula in the IAu Ln Ymin derL DichalkogenocarbamatY Dichalkogenolate, Merkaptoisotrithionen 1m 1 contains. The emulsions are suitable for making black and white photographic and color materials.

Description

mean, contains.

Field of application of the invention

The invention relates to a photographic silver halide emulsion which is suitable for the production of photographic black and white and color materials.

Characteristic of the known state of the art

The use of gold compounds in the preparation of silver halide emulsions is well known, the

Applications and effects are extensive. They include sensitization, clarification and i

Stabilization effects, as well as effects in the spectral Sonεibiiisierung and on the reciprocity behavior of photographic

Silver.

The literature and patents include a number of gold compounds for chemical sensitization such as:

HAuCI ₄₁ AuCI ₃ (DE-PS 1185481, DE-PS 1174156), KAu (SCN) ₂ , KAuCI ₄ (US-PS 3320069) and gold sulfide (US-PS 3408196).

Furthermore, complex compounds of gold are known, which as ligands mercapto or mercapto glucose compounds

(GB-PS 1160728, GB-PS 1184138), substituted thioureas, thiosemicarbazide, acetonitrile, thiazolidine (M.Süzs,

Schröter, J. Reinhold, H. Zwanziger, E. Hoyer, J. Signal AM5 [1977] 6,449-455). Triphenylphosphine. trimethyl phosphite

(J. Hardening, Chr. Schröter, J. Reinhold, H. Zwanziger, W.Dietzsch, E. Hoyer, J. Signal AM8 (1980) 2.95-101), thioethers,

Amino acids, thioamino acids, mercaptoamino acids or amines (DD-WP 249106) have.

Stabilization and clarification of photographic silver halide emulsions or materials is achieved by compound such as

KAuCI ₄ , AuCl ₃ , KAu (SCN) ₄ , (C ₂ H ₅ N) AuCl ₃ χ HCl, Au (C ₂ Hg) ₂ Br, and benzothiazoles condensed by gold complexes, quinolines

or cyclic olefins (US Patent 2597915, US Patent 2597856, US Patent 4353981, DE-PS 1251760) causes.

The known compounds may also be used in combination with other additives, such as sulfur sensitizers,

Reducing agents, polyvalent metal ions (DD-WP 215409, DD-WP 215410) or precious metal compounds (DD-WP 231430,

DD-WP 231431, DD-WP 237230, DE-PS 964561, US-PS 2540086) are applied. ;

Of the known compounds shown, only a few are of practical importance. To achieve high '

Sensitivities in modern photographic materials are also limited to these gold compounds, so that os

it is necessary to search for new substances that bring advantages in the sensitometric parameters.

Aim of the invention ^;

The object of the invention is a photographic emulsion with improved photographic properties. !

Explanation of the essence of the invention

The object of the invention is to provide a photographic silver halide emulsion with improved sensitivity,!

low minimum density and good durability. '

According to the invention, the object is achieved in a photographic silver halide emulsion with gold compounds which

Gold compounds of general formula,

AuL _n Y _{n, (I!}

in the

L = Dichalcogen carbamate

Y = dichalcogenolates, mercaptoisotrithione j η = 1

m = 1 j

mean, contains.

The gold compounds are easy to prepare and their synthesis is described in the literature (van der Linden, JGM Rec.Trav. Chiin.90, 1027 [1971], van der Linden, JGM; von der Roer, HGJ Inorg. Chim. Acta 5,254 [ 1971); Friedrich, H. Diploma thesis, Karl Marx University, Leipzig [1984]).

The use of these compounds in photographic silver halide emulsions achieves improved low fog sensitivity, gradation enhancement, and emulsion stabilization. The noble metal compounds stable to atmospheric oxygen and humidity are readily soluble in water-miscible solvents.

The compounds according to the invention may be added to the silver halide emulsions throughout the course of the emulsion preparation. It proves to be favorable to add the complexes between the beginning of the physical ripening and the pouring. Depending on the composition and the production conditions of the emulsion, the compounds in concentrations of 10 to ~ ^s to 10 ~ ² moles of gold per mole of silver are employed. The use of the compound may be in all types of emulsions, such as silver bromide emulsions, silver chloride emulsions. Silver bromochloride emulsions, silver chlorobromide emulsions, silver bromoiodide emulsions, silver bromide emulsion, silver bromobromide iodide emulsions. The emulsions mentioned can be prepared both by conventional methods and by double-emulsion emulsification. These may be both boiling emulsions and emulsions which are prepared in the presence of silver halide solvents such as ammonia, rhodanides, thioethers, thioamino acids, thiourea derivatives, thiosulfates, halides in high excess which accelerate physical ripening.

Also, combinations of these silver halide solvents may be wounded.

The emulsions of the present invention may be high, medium or low sensitivity black and white or color negative emulsions, positive emulsions, reverse, print out and direct positive emulsion emulsions, X-ray, photographic and scientific photo-emulsion emulsions and emulsions used for the production of materials based on silver salt or dye diffusion processes. The emulsions according to the invention may contain silver halide crystals having an average grain diameter of 0.01-5 μm, the size distribution of which may be monodisperse, narrow-distributed or broadly distributed. The silver halide crystals contained in the described emulsions can be cube-shaped crystals having / 100 / faces, octahedral crystals having / 111, 'faces, crystals having both / 100 / and / 111 / faces, twin crystals, crystals having a spherical habit and Crystals having a different surface diameter / thickness ratio (from 5: 1 to 500: 1). During the preparation of the described crystals in the emulsions according to the invention, which are used for the cited materials, various polyvalent Mbtallionen of Ni, Zn, Co, Mn, Fe, Sr, Ba, Mg u. a. and noble metal ions of Pt, Pd, Ir, Os, Rh, Ru, Re, Au, Ag, and the like. a. be added.

It is also possible to use combinations of polyvalent metal ions with one another, noble metal ions with one another, or combinations between one or more polyvalent metal ions with one or more noble metal ions.

The compounds according to the invention can be used in the emulsions in combination with other gold compounds, sulfur sensitizers, reducing agents, polyvalent metal ions, noble metal compounds and other chemical sensitizers. Furthermore, it is possible for the novel emulsions photographic additives such as clear coaters, stabilizers, spectral sensitizers, curing agents, couplers, Netzmi ?. and resistors ^r e Begießzusätze add.

The emulsions obtained according to the invention are suitable for the preparation of photographic black and white and color recording materials. They have improved properties in terms of their speed-fog ratio, their >> adation and their stability. These materials can be developed with equally good results at processing temperatures of 15 ^° C to 50 ^° C.

embodiment

A narrowly distributed Silberiodidbrom'dchloridemulsion with 10 mol% bromide and 1 mol% iodide and having an average crystal diameter of 0.42 pm is watered after physical ripening to remove soluble residual salts to a conductivity of 1800 \ xs · cm "', in several be divided parts and as shown in Table 1 with 3.2 χ 10 ^-4 mol per mol of Ag Au and according to Table 2 4.5 10 ~ χ * Au mol per mol Ag of the compounds indicated provided. the emulsions then at 45 ⁰ C, a pH of 6.5 and a pÄg value of 6.8 chemically matured.

After adding the usual Begießzusätze be cast on a support layers of the same density and dried. These are exposed behind a grayscale wedge in a sensitometer and developed in a developer of the following composition:

Monomethyl-p-amir.ophenolsulfat 5.0 g hydroquinone 6.0 g sodium 40.0 g potash 40.0 g potassium 3.0 g mitWaseerauf 1000ml refilled.

The development time is 5 min at 2O ⁰ C. After an intermediate watering in ORWO 200 is fixed in ORWO 30112min, then watered, the samples dried and measured on the densitometer. The results are summarized in Tables 1 and 2.

Table 1 compound D _min ΔΕ0.5 E 05 without Au [(N-N-diethyldithiocarbamate) (maleonitrile dithiolate)] Table 2, Compound 0.07 0.06 D _mi n +3.5 E 01 5.5 4.5 6.0 HAuCl ₄ NH ₄ IAu (SCN) ₂ ) Au [(N, N-diethyldithiocarbomat) (maleonitrile dithiolate)] 0.07 0.06 10,6 10,0 11,5

The results show the sensitometric effect of the compounds according to the invention in comparison with the chemically unripened emulsions and the emulsions sensitized with conventional gold compounds.

Claims (1)

Photographic silver halide emulsion containing gold compounds, characterized in that they
Gold compounds of the general formula "Y _{m /} L = Dichalcogenocarbamate Y = dichalcogenolates, mercaptoisotrithione
η = 1 m = 1