JPH09211820A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable fixation in a short time without forming a precipitate in a stabilizing soln. disposed behind a fixing soln. by carrying out processing with the fixing soln. contg. a specified compd. in a specified time. SOLUTION: A silver halide photographic sensitive material is processed with a fixing soln. contg. a compd. represented by the formula in 1-60sec. The amt. of the compd. is preferably regulated to 0.02-5wt.%, especially 0.1-2wt.% of the amt. of thiosulfates contained in the fixing soln. The silver halide of the sensitive material is, e.g. silver chloride, silver chlorobromide, silver bromide, silver iodobromide or silver iodide and the sensitive material is preferably a silver iodide photographic sensitive material having such a relatively high silver iodide content as >=5mol% of the silver halide content, e.g. a sensitive material for photographing. A fixing agent contained in the fixing soln. is preferably thiosulfates especially including <=70mol% ammonium thiosulfate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material which is effective in accelerating a fixing process.

[0002]

Since the time required for developing a photosensitive material for photographing such as a color negative film or a color reversal film is considerably longer than that of a photosensitive material for printing, it is necessary to speed up the processing. Is very large.

In the case of a color negative film, the silver halide used is silver iodobromide, and since the silver content is high, desilvering is difficult and the desilvering time is much longer than that of color paper. In the case of color negative film and color reversal film, to increase the bleaching power,
Bleaching and fixing are usually performed in separate baths, and various bleaching agents and bleaching accelerators have been found and are being put to practical use for bleaching.

For fixing, however, a fixing bath using a thiosulfate as a fixing agent is still the mainstream, and there are cases in which thiocyanate is used in combination and cases in which thioether is added, but the effect is small.

Further, since all of these compounds act as a solvent for silver halide, they do not function unless they are added at a high concentration, and they are industrially used in a large amount, and practically used in comparison with inexpensive thiosulfates. There is a demand for a so-called fixing accelerator, which has a low property and whose quickness is improved by adding a small amount. Although there are compounds such as thiourea, they have some effects as bleaching accelerators and bleach-fixing accelerators, but their fixing promoting effect is low. Furthermore, since these compounds have low stability with silver, when they are treated for a short period of time, the ones having a low silver complex stability of silver thiosulfate complex salts are brought into the stabilizing solution in the next step, and are processed. There is a problem that a precipitate is formed in the material or the stabilizing solution.

The present invention has been made in view of the above situation, and an object thereof is a silver halide photographic light-sensitive material capable of carrying out a fixing process in a short time without producing a precipitate in a stabilizing process solution following a fixing solution. Is to provide a processing method.

[0007]

The above object of the present invention is to use a fixing solution containing a compound represented by the general formula (1) for 1 to 60 seconds for processing a silver halide photographic light-sensitive material. This is accomplished by a method of treating the material, in which at least a portion of the stabilizing treatment solution is added to the fixing solution.

That is, the present inventors have made the fixing solution contain a compound represented by the general formula (1) (hereinafter, also referred to as the compound of the present invention), so that the fixing processing time is as short as 60 seconds or less. It was found that even if the time is passed, no precipitation is caused in the stabilizing solution, and the present invention has been achieved.

The present invention will be described in detail below.

Specific examples of the compound represented by the general formula (1) in the present invention are shown below, but the invention is not limited thereto.

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

Among the above compounds, the compounds preferably used for the purpose of the present invention are (1-9) and (1-1)
0), (1-13) and (1-31), particularly preferably (1-10) and (1-13), most preferably (1-10).

In the present invention, it is contained in the fixer,
The total weight of the compound of the general formula (1) is preferably 0.02% by weight or more and 5% by weight or less, more preferably 0.1% by weight or more and 2% by weight or less, based on the weight of thiosulfate. It is preferable.

The present invention solves the problem of precipitation in a light-sensitive material or a stabilizing solution which occurs when the fixing processing time is set to 60 seconds or less, but the processing time is 3 to 50 seconds, more preferably 5 seconds. The effect is fully demonstrated when it is set to ~ 40 seconds.

Examples of the silver halide of the light-sensitive material to be processed include silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodide, etc. It is preferable that the silver iodide photographic light-sensitive material has a relatively high silver iodide content of 5 mol% or more of the silver halide of the light-sensitive material for use.

The fixing solution according to the present invention contains a so-called fixing agent.

As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt, for example, potassium thiosulfate, sodium thiosulfate, thiosulfate such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanic acid. Examples thereof include thiocyanates such as ammonium, thiourea thioethers and the like, but thiosulfates are preferable from the viewpoint that the effects of the present invention can be fully exhibited, and more preferably thiosulfates among thiosulfates. Ammonium sulfate is 70 mol% or less. The ratio of ammonium thiosulfate in this thiosulfate is preferably 50 mol% or less, and particularly preferably 2 mol%.
It is 0 mol% or less.

In addition to these fixing agents, further fixing solutions include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. A pH buffer consisting of various salts such as, and alkylamines, polyethylene oxides, and the like, which are known to be usually added to a fixing solution, can be appropriately added.

The fixing agent is used in an amount of 0.1 mol or more per liter of the processing liquid, preferably 0.6 to 4 mol, particularly preferably 0.9 to 3.0 mol, and particularly preferably 1 mol. It is used in the range of 0.1 to 2.0 mol.

In the present invention, air or oxygen may be blown in the treatment bath and in the treatment replenisher storage tank in order to increase the activity of the treatment liquid, if desired, or a suitable oxidizing agent such as peroxide may be used. Hydrogen, bromate, persulfate and the like may be added appropriately.

The pH of the fixing solution of the present invention is preferably 4-8.
Used in the range.

The fixing solution of the present invention can contain a sulfite and a sulfite-releasing compound, and the compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, and metabisulfite. Examples thereof include potassium, sodium metabisulfite, and ammonium metabisulfite. Further, sodium formaldehyde bisulfite, sodium acetaldehyde bisulfite, sodium propionaldehyde bisulfite, sodium butyraldehyde bisulfite, sodium succinic aldehyde bisulfite, glutaraldehyde bis sodium bisulfite, β-methylglutaraldehyde bis sodium bisulfite, maleic acid. Dialdehyde bis sodium bisulfite and the like can also be used.

These sulfites and sulfite-releasing compounds are used as sulfurous acid in an amount of 0.1 mol or more, preferably 0.12 to 0.55 mol / l, and further 0.15 per 1 l of the fixing solution.
˜0.50 mol / l, especially 0.20 to 0.40 mol / l.

The fixing treatment tank in the present invention may be one tank or two or more tanks, but the effect of the present invention can be effectively exhibited especially in the case of one tank.

By containing the compound of the present invention in the fixing solution, the processing solution pumped out from the stabilizing tank can be introduced into the fixing solution in the fixing processing step without causing precipitation and the amount of the replenishing solution can be reduced.

Specific processing steps of the processing method according to the present invention include (1) color development → bleaching → fixing → stable, (2)
Color development → bleaching → fixing → first stability → second stability, (3) color development → bleaching → bleach-fixing → fixing → first stability → second stability.

[0030]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 In the following, the addition amount in the silver halide photographic light-sensitive material is shown in g per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

<< Photosensitive Material Sample >> A multi-layer color photographic photosensitive material sample was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

First Layer: Antihalation Layer (HC-1) Black Colloidal Silver 0.22 UV Absorber (UV-1) 0.20 Colored Coupler (CM-1) 0.05 Colored Coupler (CM-2) 0 .05 high boiling point solvent (Oil-1) 0.20 gelatin 1.3 second layer: intermediate layer (IL-1) ultraviolet absorber (UV-1) 0.01 high boiling point solvent (Oil-1) 0.01 Gelatin 1.3 Third layer: low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 1.0 Silver iodobromide emulsion (Em-2) 0.5 Sensitizing dye (S-1) ) 2.5 × 10 ⁻⁴ mol / silver 1 mol Sensitizing dye (S-2) 2.5 × 10 ⁻⁴ mol / silver 1 mol Sensitizing dye (S-3) 0.5 × 10 ⁻⁴ mol / Silver 1 mole Cyan coupler (C-4〃) 1.2 Cyan coupler (C-2〃) 0.06 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.3 Fourth layer: high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide Emulsion (Em-3) 2.0 Sensitizing dye (S-1) 2.0 × 10 ⁻⁴ mol / silver 1 mol Sensitizing dye (S-2) 2.0 × 10 ⁻⁴ mol / silver 1 mol Sensitizing dye (S-3) 0.1 × 10 ^-4 mol / silver 1 mol Cyan coupler (C-1〃) 0.15 Cyan coupler (C-2〃) 0.018 Cyan coupler (C-3〃) 1 .15 Colored cyan coupler (CC-1) 0.015 DIR compound (D-2) 0.05 High boiling point solvent (Oil-1) 0.5 Gelatin 1.2 Fifth layer: intermediate layer (IL-2) Gelatin 0.4 Sixth layer: low-sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.9 Sensitizing dye (S-4) 5.0 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-5) 1.0 × 10 ^-4 mol / silver 1 mol Magenta coupler (M-1〃) 0.3 Magenta coupler (M-2〃) ) 0.2 Colored magenta coupler (CM-1) 0.05 DIR compound (D-3) 0.015 DIR compound (D-4) 0.020 High boiling point solvent (Oil-2) 0.5 Gelatin 1.0 7th layer: Intermediate layer (IL-3) Gelatin 0.8 High boiling point solvent (Oil-1) 0.2 8th layer: High sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 1 .2 Sensitizing dye (S-6) 1.5 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-7) 2.5 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-8) 0.5 × 10 ^-4 mol / 1 mol of silver magenta coupler (M-2〃) 0.06 magenta coupler (M-3〃) 0.18 colored Zenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling point solvent (Oil-3) 0.5 Gelatin 1.0 9th layer: Yellow filter layer (YC) Yellow colloidal silver 0. 1 Color Contamination Inhibitor (SC-1) 0.1 Gelatin 0.8 Tenth Layer: Low Sensitivity Blue Sensitive Emulsion Layer (BL) Silver Iodobromide Emulsion (Em-1) 0.25 Silver Iodobromide Emulsion (Em -2) 0.25 sensitizing dye (S-10) 7.0 x 10 ^-4 mol / silver 1 mol Yellow coupler (Y-1〃) 0.6 Yellow coupler (Y-2〃) 0.12 DIR compound (D-2) 0.01 High boiling point solvent (Oil-3) 0.15 Gelatin 1.0 11th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.45 Iodine silver bromide emulsion (Em-1) 0.20 sensitizing dye (S-9) 1.0 × 10 -4 mol / 1 mole sensitizing dye (S-10) 3.0 × 10 -4 mol / 1 mol of silver Yellow coupler (Y-1〃) 0.36 Yellow coupler (Y-2〃) 0.06 High boiling solvent (Oil- 3) 0.07 Gelatin 1.1 12th layer: 1st protective layer (Pro-1) Fine grain silver iodobromide emulsion (average grain size 0.08 μ, AgI 2 mol%) 0.4 Ultraviolet absorber (UV-1 ) 0.10 UV absorber (UV-2) 0.05 High boiling point solvent (Oil-1) 0.1 High boiling point solvent (Oil-4) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger ( HS-2) 0.2 Gelatin 1.0 Surfactant (Su-1) 0.005 Alkali-soluble matting agent (average particle size 2 μ) 0.10 Cyan dye (AIC-1) 0.005 Magenta dye ( AIM-1) 0.01 sliding Agent (WAX-1) 0.04 Gelatin 0.8 In addition to the above, coating aids Su-2, dispersion aids Su-3, hardeners H-1 and H-2, and antifungal agents are provided for each layer. DI-1,
Stabilizer Stab-1, antifoggants AF-1 and AF-
2 was added. The emulsions used are as follows.

Em-1: Average grain size 0.46μ, average silver iodide content 7.5% Monodisperse surface low silver iodide-containing emulsion Em-2: Average grain size 0.32μ, average iodide Silver content 2.0% Monodisperse emulsion of uniform composition Em-3: Average grain size 0.78 µ, average silver iodide content 6.0% Monodisperse surface low silver iodide-containing emulsion Em- 4: Average grain size 0.95 μ, average silver iodide content 8.0% Monodisperse surface low silver iodide content emulsions Em-1, Em-3 and Em-4 are disclosed in JP-A-60-138.
It is a silver iodide emulsion having a multi-layer structure prepared mainly with reference to Nos. 538 and 61-245151, and which is mainly composed of octahedra. Further, Em-1 to Em-4 are all (particle size) /
The average value of (particle thickness) was 1.0, and the breadth of the particle distribution was 14, 10, 12 and 12% (variation coefficient), respectively.

[0035]

[Chemical 6]

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

The obtained film sample was loaded into a camera for actual exposure, and a running process was carried out under the following conditions until the fixing replenisher was replenished in an amount of 3 times the capacity of the fixing tank tank in 20 days.

Processing step Processing time Processing temperature (° C.) Replenishment amount (ml / light-sensitive material 1 m ² ) Color development 3 minutes 15 seconds 38 625 Bleaching 45 seconds 37 250 Fixed 1 minute 30 seconds 37 600 Stability 60 seconds 37 600 Drying 60 seconds 70-However, 3 stabilizing tanks have counter currents (20 seconds each,
3 tanks). The crossover time of each process was 3 seconds.

The composition of the treatment liquid used is shown below.

<< Color Developer >> Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 4 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3- Methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulphate 4.8 g Potassium hydroxide 1.2 g Add water to make 1 liter and adjust to pH 10.06 with potassium hydroxide or 50% sulfuric acid. .

<< Color Development Replenisher >> Potassium carbonate 40 g Sodium hydrogen carbonate 3 g Potassium sulfite 7 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxy Ethyl) aniline sulphate 6.0 g Potassium hydroxide 2 g Water is added to make 1 liter and pH is adjusted to 10.11 with potassium hydroxide or 20% sulfuric acid.

<< Bleaching Solution and Bleaching Replenishing Solution >> 1,3-Propanediamine tetraacetic acid ferric ammonium salt 150 g Ammonium bromide 100 g Water is added to make 1 liter, and the pH is adjusted to 4.3 using aqueous ammonia or glacial acetic acid. .

<< Fixing Solution and Fixing Replenishing Solution >> Ammonium thiosulfate 200 g Additive (listed in Table 1) Listed in Table 1 Ammonium sulfite 10 g Ethylenediaminetetraacetic acid disodium 5 g Water was added to make 1 l, and pH was adjusted to 7 with acetic acid and aqueous ammonia. Adjust to 2.

<< Stabilizer and Stable Replenisher >>

[0054]

Embedded image

5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g Water was added to make 1 L, and the pH was adjusted to 7.0 with aqueous ammonia and 50% sulfuric acid.

The additives in the fixer and fixer replenisher were changed as shown in Table 1 to carry out the running process.

After the running treatment, the state of precipitation in the stabilizing solution in the first tank was observed. In addition, the running solution in each processing tank was pumped out, the fixing time was changed as shown in Table 1, hand development was performed using the same photosensitive material sample, and the amount of residual silver in the unexposed area of the processed film was determined by fluorescent X-ray. It was measured by the method. The results are shown in Table 1.

[0058]

[Table 1]

As is clear from the results shown in Table 1, when the fixing solution contains the compound of the present invention, there is no difference at 90 seconds.
Even if the treatment is carried out for a short time of 60 seconds or less, good fixing performance is obtained, precipitation does not occur in the first tank of the stabilizing solution, and the effects of the present invention are effectively exhibited.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the fixing treatment time was 15 seconds and the additives were changed as shown in Table 2. Table 2 shows the results.

[0061]

[Table 2]

From this, it is understood that even if any of the compounds of the present invention is added and treated for a short time, the fixing performance is excellent and no precipitate is formed in the stabilizing solution.

Example 3 The stabilizing solution overflow was poured into the fixing solution, and the additives in the fixing solution were replenished so as to be as shown in Table 3 and the other fixing solution composition to be almost the same as in Example 1. The same evaluation as in Example 1 was performed by performing the treatment while performing the treatment. The results are shown in Table 3.

[0064]

[Table 3]

As a result, in a system using a known fixing accelerator (thiourea), when an overflow of the stabilizing solution is poured into the fixing solution, the desilvering rate is deteriorated and a precipitate is generated in the stabilizing solution. It is understood that when the compound of (1) is added to the fixing solution, the desilvering performance is excellent even if the processing is speeded up, precipitation is not generated in the stabilizing solution, and the replenishment amount can be reduced.

Example 4 Experiment No. In 2-3, an experiment was performed in the same manner as in Example 1 except that the addition amount of the compound 1-10 was changed as shown in Table 4. The results are shown in Table 4.

[0067]

[Table 4]

From this, it is understood that a more preferable effect can be obtained when the addition amount of the compound of the present invention to the thiosulfate is within the above-mentioned recommended value range.

[0069]

According to the present invention, the fixing process can be speeded up without forming a precipitate in the stable processing solution.

Claims (2)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material, comprising a step of processing for 1 to 60 seconds using a fixing solution containing a compound represented by the following general formula (1). Embedded image 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein at least a part of the stabilizing solution is added to the fixing solution.