JPH0126048B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to concentrates containing silver halide and suitable for use in dilution as developers of imagewise exposed photographic recording materials.

Silver halide-containing photographic materials are mainly developed in alkaline media, using o- or p-dihydrobenzene, aminophenols, diaminobenzenes, pyrazolidinones, redouktones or hydroxylamine derivatives as developer substances. Developer solutions often also contain additives such as stabilizers such as sulfates, antifoggants and buffers. Furthermore, it is known that in certain cases photographic materials are developed in the presence of silver halide solvents. Such silver halide solvents include, for example, mercapto compounds, thioethers, thioamides, or compounds with an acidic -CH- group, such as organic divalent sulfur compounds such as bis-methylsulfonylmethane, and also rhodanic acid salts. , there are high concentrations of sulfites, especially thiosulfites. Developers containing such additives are known as particulate developers and internal particle developers. (See E. Muzter, “Negative and Positive Processing Techniques”, Springer 1955, pp. 158-159)
The development of latent silver nuclei within the grains is of particular significance in reversal development methods in which thiocyanate is often added to the first developer. A broad implementation of this process is described in U.S. Pat. No. 3,857,710 or in G. Heist's "One Bath Manual", Morgan 1960. Another implementation of this method is published in German publication 2547720
This is a mask developer for the silver color bleaching method as described in the issue.

This large number of developers, however, has the disadvantage that they more or less rapidly reduce the silver halide eluted from the photographic material in a complex manner. Therefore, a contamination occurs in the developer and after a while turns into a silver sludge, which sticks to the photographic material as well as to some parts of the developer tools. This silver slurry is particularly disadvantageous in continuous operation equipment.
Attempts to find suitable measures against this silver mud formation have not been successful.

DE 24 37 353 proposes the use of 1-phenyl-5-mercaptotetrazole derivatives in X-ray film developers for silver precipitation in developer solutions. U.S. Patent No. 3173789 and German Patent Publication No. 1175077 and German Published Application No. 1175077
No. 2003414 describes that a heterocyclic mercapto compound is added, and German Published Publication No. 1909743 describes that an aliphatic mercapto-carboxylic acid is added to the treatment solution to prevent the formation of silver mud. U.S. Patent No. 3318701
α-Liponic acid in the issue, also German Open Gazette
No. 2040801 has 4-acylamino-1,2,3-
Triazoline-5-thione has been proposed for preventing sludge formation. These substances are mostly added in amounts of 5 to 5000 mg per liter of developer.

Although these proposed additives can retard silver mud development for a period of time, they have various undesirable side effects. Substances with good transparency properties have a considerable influence on developer properties. In multilayer color materials, the sensitivity is reduced, especially of the top layer.
In the mask development of silver color bleaching materials, interference with the mask effect appears. Other materials are unstable in the developer and rapidly lose effectiveness or decompose due to air oxidation, producing malodorous and/or harmful by-products. All these drawbacks have considerably hindered and in many cases made impossible the practical application of the transparency-retaining materials proposed so far. DE 2640659 describes a developing method in which specific organic di- or tri-sulfides are used at the end to keep the developer solution transparent.

These di- and tri-sulfides are most well suited for clarity preservation and prevention of silver mud formation in photographic developers; however, they are difficult to obtain synthetically and moreover require a considerable amount in the developer to achieve the desired effect. The disadvantage is that it requires a large amount.

It is an object of the present invention to establish new developer precursors in which the obstacles to photographic development are largely eliminated in order to prevent dark coloration and sludge formation in photographic developers.

The present invention provides a silver halide developable compound, a water-soluble silver halide solvent, (a) a general formula where R represents phenyl or lower alkyl,
The compound represented by and (b) general formula Here R represents phenyl or lower alkyl,
M represents hydrogen or an alkali metal, and is a non-aqueous liquid or paste concentrate consisting of a compound of the formula or an amino(lower)alkanethiosulfonic acid or an alkali metal salt thereof.

In the present invention, the above (a) and (b) are used as organic sulfur compounds.
Combine the two types.

In the general formula, (lower) alkyl includes common lower alkyl groups such as methyl, ethyl, n-propyl, n-butyl, and n-amyl. Examples of alkali metals include sodium and potassium.

The concentrates contain conventional silver halide developing compounds such as dihydroxybenzene, aminophenol, diaminobenzene, pyrazolidinone, redowactone or hydroxylamine derivatives.

Common water-soluble silver halide solvents include, for example, thioethers or thioamides, rhodanhydrogen salts, high concentrations of sulfites, preferably thiosulfates. When the concentrate is diluted to form a developer, sulfite is generally prepared in an amount of more than 20 g/in some cases, even in a small amount such as 10 to 20 g/in, and thiosulfate is prepared in a concentration of 0.1 to 200 g/in. Added to aqueous solution.

When diluted in a developer, the thiosulfate concentration is preferably 10 to 200 g/for use in one bath, and 0.1 to 10 g/for mask development of silver color bleaching materials.
It is. In this case, compounds having formulas (9) to (15) are particularly suitable as sulfur compounds. Sulfur compounds are also inverted, chromogen, and roentgen.
Alternatively, it can be used in developing formulations for black-and-white film materials.

Components (a) and (b) are 0.01 to 1 g/or 0.1
It is preferable to use it so that it is present in the aqueous developer solution in an amount of 10 to 10 g.

Suitable concentrates therefore contain, when diluted 2 to 25 times, 0.1 to 20 g of silver halide developable compound, 0.1 to 200 g of silver halide solvent and 0.05 to 10 g of component (a). and (b) having a molar ratio of (a):(b) from 5:1 to 1:100, preferably from 1:1 to 1:20.

A developer solution can be produced by diluting the concentrate of the invention with water, optionally mixed with an organic solvent.

Concentrates can be liquid or pasty, and in some cases solid.

The developer formulations obtained from the concentrates of the present invention can be used to develop silver color bleaching materials exhibiting a layer structure suitable for reducing undesirable residual color densities.

In particular, they can be bleached imagewise by exposure, silver development, color bleaching, silver bleaching and fixing, each in at least two layers, with an absorption maximum of three primary colors red,
Relating to a method for producing masked reduced color positives using photographic materials having dyes corresponding to each of green and blue, each dye being accompanied by a spectrally sensitive silver halide emulsion layer . In this case a silver halide emulsion layer produced at least partly from silver iodide is attached to the dye, which has to compensate for the undesirable residual color density of the dye in the above-mentioned materials, and in this case one other layer has a silver halide emulsion layer. at least a second dye and an iodine ion-free silver halide emulsion having a primary color density compatible with the compensated extra color density of the first dye; and a layer adjacent to the layer containing the second dye; indicates a colloidal species capable of separating silver metal from soluble silver complexes, and there is a separation layer between the layer containing this species and the dye layer whose residual color density is to be compensated, and the material is exposed. The post-processing silver development bath contains a ligand capable of forming a water-soluble diffusible silver complex and a mixture of compounds having formula (1) or (2) and (3). Particularly preferred are mixtures of compounds having formulas (13) and (15).

The mixture of mercapto compound and Bunte salt used in the present invention is particularly excellent in preventing silver separation in a developer for a long time. Moreover, in contrast to the anti-sludge agents previously used, the mixture of (a) and (b) used in the present invention is inert in photographic practice and is very stable in the usual sense, which shows that This is preferable for the continuous development operation described above.

In the following examples, all parts and percentages are by weight.

Example 1 In a red sensitized subbing layer on a pigmented cellulose acetate support, the formula: A blue-green image dye with the formula: In the violet dye with the formula: A photographic material for a silver color bleaching process was produced containing a yellow dye with .

The photographic materials used were constructed as follows. (German Publication No. 2036918, 2132836 and
(See No. 2547720) Gelatin protective layer Blue-sensitive, non-iodide, AgBr emulsion yellow dye (103) + blue-sensitive non-iodide, AgBr emulsion yellow Filter: Yellow Ag-hydrosol (40 mg/m ² ) Green-sensitive AgBr/ AgI-emulsion purple dye (102) + green-sensitive AgBr/AgI-emulsion interlayer (gelatin) blue-green dye (101) + red-sensitive AgBr/AgI-emulsion red-sensitive AgBr/AgI-emulsion cellulose acetate support, White Opaque Backing Layer, Gelatin This layer configuration allows correction of the blue extracolor density of the blue-green and violet dyes by additional bleaching of the yellow image dye in accordance with other two-image dye bleaches. (The blue-sensitive layer has a yellow dye-free iodide emulsion; the remaining dye layers have iodide-containing emulsions.) The budded layer is adjacent to the yellow dye layer. This is separated from the violet layer by a colorless emulsion layer which additionally contains a yellow overdye (a green-sensitive AgI-containing emulsion layer and at the same time a separating layer).

The iodide-containing emulsion layer has crystals containing 2.6 mole percent silver iodide and 97.4 mole percent silver bromide. The image dye is used in such a concentration that its permissible concentration is always 2.0, ie the total silver content of a 22 micron thick layer is 2.0 g/m ² .

Color transparencies were printed onto this material in an enlarger. The exposed material was treated according to the following criteria (French Patent No. 2247755). In this case, the treatment temperature was 30°C.

1 Silver image bath for 3 minutes A paste-like concentrate having the following concentration when diluted 10 times with water was prepared. Then, before use, it was diluted to create a developer.

Ethylenediaminetetraacetic acid tetrasodium salt
2g/ Potassium hydroxide 85% 30g/ Boric acid 16g/ Potassium metabisulfite 26g/ 1-phenyl-3-pyrazolidinone 0.35g/ Hydroquinone 5g/ Benztriazole 0.8g/ Potassium bromide 2g/ Anhydrous sodium thiosulfate 0.8g/ Formula ( 104) 0.5g/ Compound (105) 0.85g/ 2 Wash with water for 1 minute 3 Bleach bath for 5 minutes Sulfamic acid 100 g / Sodium m-nitrobenzolesulfonate 10 g / 1-thioglycerin 1 ml / Potassium iodide 6 g / 2,3,6-trimethylquinoxaline 2 g / 4 Wash with water 1 5 minutes Fixing bath 4 minutes Ammonium thiosulfate 250g / Potassium metabisulfate 50g / Potassium hydroxide 85% 20g / 6 Washing 6 minutes Total operating time 20 minutes Test printing of the transparencies obtained after drying reproduces the original tones and is accurate It was particularly excellent in color reproduction.

Development requires longer times due to the addition of two compounds (with formulas (104) and (105)). The developer remained clear even after multiple color stretching operations, ie, no silver metal separation occurred.

A developer obtained from a concentrate containing only the compound having formula (104) remains transparent for a long enough time, but the developer properties change and the yellow blur in the shadows flattens out in the developed color photographic material, causing The balance of the blur is lost. Color prints processed with this developer do not give a satisfactory yellow tone. Moreover, dark image areas once had a blue tint.

A diluted concentrate containing only the compound having formula (105) was colored shortly after use, and metallic silver was separated.

Good results were also obtained using other combinations of mercaptans and Bunte salts shown in the table above in place of the mixture of compounds having formulas (104) and (105).

Example 2 A silver color bleaching material was treated according to the method of Example 1, except that the formula: A concentrate was prepared by adding compounds with , and this was diluted to make a silver developing bath.

The development time was 2 minutes at 30°C. Test prints with good quality images were obtained after drying. No change in image quality or contamination of the solution was observed even with repeated use of the developer solution (total of 0.1 m ² of material per liter of solution).

Example 3 A concentrate with the following formulation was prepared.

Potassium carbonate 30g Sodium sulfite 100g Potassium bromide 3g Hydroquinone 40g Ethylenediamine-tetraacetic acid disodium salt 1.5g Potassium hydroxide 17g This was divided into two equal parts, 0.5g of the compound having formula (104) was added to the former (A), and the latter (B) to 2-aminoethane-
0.5 g of thiosulfonic acid and 0.5 g of a compound with formula (104) were added.

At the time of use, water was added to the thus obtained concentrates A and B to make up 500 ml each.

Both solutions were used to develop black and white camera film. Part A remained transparent for a while, but soon became cloudy due to silver mud. The developability of this solution was changed as in Example 1 above. On the contrary, part B remained transparent and maintained better developability even after long-term use.

Example 4 A concentrate was made with the following formulation: 2 g of 4-methylaminophenol sulfate, 5 g of hydroquinone, 100 g of sodium sulfite (anhydrous), 3 g of borax, 0.5 g of the compound with formula (104), and 0.85 g of the compound with formula (105). . Immediately before use, water was added to bring the total volume to 1.

Use this solution in the tank to make 20 black and white camera films.
Developed at ℃ for 6 minutes. After developing all 10 rolls of 135-inch film with 36 exposures each, the solution began to run out and it became necessary to replace it with new solution or add new solution. Contrary to the developer solution in which compounds having formulas (104) and (105) were not present, no trace of silver mud was observed up to this point.

Claims (1)

[Claims] 1 Silver halide developable compound, water-soluble silver halide solvent, and (a) general formula where R represents phenyl or lower alkyl; and (b) a compound represented by the general formula Here R represents phenyl or lower alkyl,
M represents hydrogen or an alkali metal, and consists of a non-aqueous liquid, paste, or solid material containing a compound represented by or an organic sulfur compound formed by combining amino (lower) alkanethiosulfonic acid or an alkali metal salt thereof. A developing concentrate characterized by: 2 When the concentrate is diluted 2 to 25 times, each component has the following relationship: 0.1 to 20 g of silver halide developable compound/
Silver halide solvent 0.1 to 200g/component
The molar ratio of (a):(b) is 5:1 to 1:100, and component (a) and
The developing concentrate according to claim 1, characterized in that the total of (b) satisfies the relationship of 0.05 to 10 g/.