JPH07113764B2 - Method for processing silver halide color photographic light-sensitive material capable of improving the color recovery of cyan dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide color photographic light-sensitive material (hereinafter
It is referred to as a "photosensitive material"), and more specifically to a bleach-fixing method using a bleach-fixing solution.

[Conventional technology]

Conventionally, as a processing step for obtaining a dye image from an imagewise exposed light-sensitive material, metallic silver is oxidized by a bleaching agent (oxidizing agent) in the desilvering step after the color developing step, and further remains unreduced in color developing. Desilvering is carried out by fixing together with the silver halide, and subsequently, a washing step, a washing alternative stabilizing step, a stabilizing step and the like are provided.

As the desilvering process, there is a bleach-fixing bath treatment method for completing bleaching and fixing in one step for the purpose of speeding up and simplifying the processing, as opposed to a method of performing bleaching and fixing in separate processing steps. Has been done.

When an inorganic bleaching agent is used as a bleaching agent in a bleach-fixing bath, its oxidizing power is too strong and it is difficult to mix it with a silver halide solvent in the same processing solution. Organic acid metal complex salts such as are used as bleaching agents.

However, since the bleach-fixing solution using an organic acid metal complex salt as a bleaching agent has a weak oxidizing power, it has a drawback that the bleaching rate (oxidation rate) of the image silver (metallic silver) formed in the developing step is slow. There is. Therefore, in a bleach-fixing bath which is usually used and consists of one tank, desilvering failure and color restoration failure occur when the processing is accelerated.

As a technique for solving such a problem, Japanese Patent Laid-Open No. 62-91952
In No. 1, the processing was carried out in at least two bleach-fixing baths, which were replenished in a countercurrent method for the purpose of quick and sufficient desilvering. Of 45% or less is disclosed. However, this technique has a problem that the cyan dye has a large recoloring defect in a short time.

[Problems to be solved by the invention]

Therefore, an object of the present invention is to provide a bleach-fixing method for a light-sensitive material capable of sufficiently desilvering in a rapid process and having improved cyan dye recolorability.

[Means for solving problems]

As a result of earnest research, the present inventor has found the most preferable time distribution of the bath when the bleach-fixing bath is a counter current system, and arrived at the present invention.

That is, the processing method of the light-sensitive material of the present invention is a method of processing the light-sensitive material with a bleach-fixing solution of a multi-tank counter current system after color development, and the bleach-fixing time until the final tank of the bleach-fixing tank is changed. 55% of the bleach-fixing time, and the silver concentration of the final bleach-fixing tank is 1/2 that of the first bleach-fixing tank.
It is characterized by the following.

In a preferred embodiment of the present invention, the bleaching agent in the bleach-fixing solution is a ferric organic acid complex salt, and its concentration is 0.25 mol / l or more, more preferably 0.25 to 1.0, further preferably 0.3 to 0.
8, the ferric organic acid complex salt is ethylenediaminetetraacetic acid ferric complex salt, and the pH of the bleach-fixing solution is in the range of 4.5 to 6.5, or the ferric organic acid complex salt is diethylenetriaminepentaacetic acid secondary salt. PH of bleach-fixing solution is 6.0-8.0 with iron complex salt
The embodiment which is the range of is mentioned.

Further, as a preferred embodiment of the present invention, there is an embodiment in which the bleach-fixing time until the photosensitive material enters the final bath of the bleach-fixing bath is 55 to 95% of the total bleach-fixing time.

Further, as a preferred embodiment of the present invention, an embodiment in which a bleach-fixing solution contains a bleaching accelerator is mentioned.

Hereinafter, the present invention will be described in detail.

The bleach-fixing method of the present invention is one in which the bleach-fixing step in the processing of a light-sensitive material is carried out in at least two continuous bleach-fixing baths. Is sequentially introduced into the adjacent pre-stage tank and discharged from the frontmost tank. In such processing, the total bleach-fixing time (including the time required to transfer between adjacent bleach-fixing tanks) until the light-sensitive material enters the final bath, The ratio of the silver concentration in the final bath to the silver concentration in the front bath is 1/2 or less. The ratio of the former is less than 55% and the ratio of the latter is 1 /
When it exceeds 2, rapid processability, color reversion and desilvering properties are deteriorated. The latter ratio is preferably 95% or less from the viewpoint of achieving the object of the present invention to a higher degree.

The number of tanks constituting the bleach-fixing bath in the present invention may be two or more, but if there are too many, it is disadvantageous in terms of the cost and space of the processing apparatus, and the effect does not increase so much, so that it is practically 2 to 2. About 4 tanks are suitable.

Examples of the bleaching agent used in the bleach-fixing bath in the present invention include organic complex salts of iron (III) or cobalt (III), preferably ferric organic acid complex salts.

The following are typical examples of the organic acid forming the ferric acid complex salt.

(1) Diethylenetriamine pentaacetic acid (MW = 393.27) (2) Diethylenetriamine pentamethylenephosphonic acid (MW
= 573.12) (3) Cyclohexanediaminotetraacetic acid (MW = 364.35) (4) Cyclohexanediaminetetramethylenephosphonic acid (MW = 508.23) (5) Triethylenetetramine hexaacetic acid (MW = 364.35) (6) Triethylenetetramine hexamethylene Phosphonic acid (MW = 710.72) (7) Glycol ether diamine tetraacetic acid (MW = 380.3)
5) (8) Glycol ether diamine tetramethylenephosphonic acid (MW = 524.23) (9) 1,2-Diaminopropane tetraacetic acid (MW = 306.27) (10) 1,2-Diaminopropane tetramethylenephosphonic acid (M
W = 450.15) (11) 1,3-Diaminopropan-2-ol tetraacetic acid (MW
= 322.27) (12) 1,3-Diaminopropan-2-ol tetramethylenephosphonic acid (MW = 466.15) (13) Ethylenediaminedioltohydroxyphenylacetic acid (MW = 360.37) (14) Ethylenediaminedioltohydroxyphenylmethylenephosphonic acid (MW = 432.31) (15) Ethylenediaminetetramethylenephosphonic acid (MW = 43
6.13) The ferric acid complex salt of an organic acid preferably used in the present invention is not limited to these, but one kind can be arbitrarily selected from these, and two or more kinds can be used in combination as necessary. You can also

The organic acid ferric complex salt is used as a free acid (hydrogen acid salt), an alkali metal salt such as sodium salt, potassium salt, lithium salt, or ammonium salt, or a water-soluble amine salt such as triethanolamine. Preferably potassium, sodium and ammonium salts are used. These ferric complex salts may be used alone or in combination of two or more. The amount used can be arbitrarily selected, and it is necessary to select it depending on the amount of silver and the silver halide composition of the light-sensitive material to be processed.

That is, it is preferably used in an amount of 0.25 mol or more, more preferably 0.25 to 1.0 mol, and even more preferably 1 mol of the used liquid.
Used at 0.3-0.8 mol.

In addition, it is desirable that the replenisher is used as a replenisher after being concentrated to the maximum solubility so that the replenisher can be concentrated and low in replenishment.

The silver halide fixing solution contained in the bleach-fixing solution of the present invention is a compound which reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate or sodium thiosulfate, which is used in a usual fixing process. , Thiosulfates such as ammonium thiosulfate are used. These fixing agents are 5 g / l or more, preferably 50 g / l or more, more preferably 70 g / l
It can be used in an amount that can dissolve at least 1 / l.

The bleach-fixing solution according to the present invention may contain various additives in addition to the bleaching agent and the fixing agent. As an additive that contributes to the bleach-fixing property, an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, ammonium iodide, sodium iodide, potassium iodide, etc. may be contained. desirable. Also known to be added to a solubilizing agent such as triethanolamine, or an ordinary bleaching solution such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, alkylamines and polyethylene oxides. What is mentioned can be added suitably.

Further, in the bleach-fixing solution of the present invention, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
Various pH buffering agents such as sodium acetate and ammonium hydroxide may be contained alone or in combination of two or more kinds.

Furthermore, various fluorescent whitening agents, antifoaming agents or antifungal agents may be contained. In addition, hydroxylamine, hydrazine, sulfite, isomeric bisulfite, preservatives such as bisulfite adducts of aldehydes and ketone compounds, other additives and organic solvents such as methanol, dimethylformamide, dimethylsulfoxide, etc. may be appropriately contained. You can

Further, it is desirable to add a polymer or copolymer having a vinylpyrrolidone nucleus as shown in Japanese Patent Application No. 50-51803.

The bleach-fixing solution used in the present invention preferably contains a bleaching accelerator which accelerates the bleach-fixing property from the viewpoint of achieving the object of the present invention to a higher degree. Examples of the bleaching accelerator that can be preferably used in the present invention include compounds described in JP-A-62-91952. The contents of the publication can be applied to the bath to which the compound is added, the amount to be added, and the like.

The bleach-fixing solution according to the present invention is preferably used usually at pH 2.0 to 10.0, more preferably at pH 3.0 to 9.5, and most preferably at pH 4.0 to 9.0. Processing temperature is 80 ℃
It is preferably used below, more preferably 55 ° C. or lower, and most preferably 45 ° C. or lower to suppress evaporation and the like. The bleach-fix processing time is preferably within 8 minutes, more preferably within 6 minutes.

In the processing method of the present invention, the bleach-fixing method of the present invention is preferably carried out immediately after color development, but after the color development, bleach-fixing processing of the present invention is carried out after washing, rinsing or stopping. You may Further, the bleach-fixing treatment of the present invention can be carried out after the pre-fixing treatment after the color development, and in this case, the bleaching accelerator may be contained in the pre-fixing treatment.

After the bleach-fixing treatment of the present invention, the stabilizing treatment may be carried out without washing with water, or may be washed with water and then stabilized. In addition to the above steps, various auxiliary steps such as hardening, neutralization, black-and-white development, reversal, washing with a small amount of water, etc. may be added as necessary.

The bleach-fixing solution is preferably subjected to an oxidation treatment in order to restore the reduced form of the iron complex salt generated in the bleach-fixing solution to an oxidant. As the oxidation treatment, for example, a known air oxidation treatment step is applied. can do.

The light-sensitive material to which the present invention is applied is not particularly limited in terms of silver halide (composition, grain size of silver halide grains, etc.), additives and the like, and a normal color negative film, color paper (including color reversal paper) The photosensitive materials to which the processing method of the present invention is applied include
Silver iodide is contained in at least one of the silver halide emulsion layers in an amount of 0.5 mol% or more, preferably 3 to 10 mol%, more preferably 5 mol% or more.
It is preferable that the light-sensitive material has a silver halide grain content of ˜8 mol% from the viewpoint that the object of the present invention can be achieved to a higher degree.

The silver halide grain containing 0.5 mol% or more of silver iodide has a silver halide iodide content of 0.5 mol% or more as the average silver halide composition of the grain. It is preferably a silver halide grain.

In the processing method of the present invention, silver halide grains having a silver iodide content of 0.5 mol% or more are present in at least one layer of the silver halide emulsion layer (a preferred embodiment of the silver halide grains is a core-shell type halogen compound as described above). It is applicable to at least all silver halide color photographic light-sensitive materials containing silver halide grains and / or tabular silver halide grains, and the halogen containing silver halide grains having a silver iodide content of 0.5 mol% or more. The silver halide emulsion layer may be all or one of the silver halide emulsion layers on the support.

For the light-sensitive material and the bleach-fixing solution in the invention, reference can be made to JP-A Nos. 62-19851, 61-261741 and 62-91953.

In order to reduce the silver concentration in the final bath of the bleach-fixing bath of the present invention to 1/2 or less of the silver concentration in the first bath of the bleaching constant bath, the light-sensitive material to which the method of the present invention is applied is halogenated. When the silver composition contains 0.5 mol% or more of silver iodide, the concentration of the ferric organic acid complex salt of the bleach-fixing solution replenisher is 0.3 mol / l or more, and the replenishing amount is ² ml per 100 cm ² of the light-sensitive material / 100 cm 2. The silver concentration of the present invention can be obtained by setting the range to 5 ml.

Further, the cyan dye-forming coupler of the present invention, which is effective in the effect of color reversal, includes known naphthol couplers and phenol couplers. Specific examples of cyan couplers that can be advantageously used include British Patent Nos. 1,038,331 and 1,543,040, JP-B-48-36894, JP-A-48-59838, 50-137137 and 5
1-146828, 53-105226, 54-115230, 56-292
No. 35, No. 56-104333, No. 56-126833, No. 57-133650
No. 57, No. 57-155538, No. 57-204545, No. 58-118643,
59-31953, 59-31954, 59-59656, 59-124
341, 59-166956, U.S. Pat.Nos. 2,369,929, 2,4
23,730, 2,434,272, 2,474,293, 2,698,79
No. 4, No. 2,772,162, No. 2,801,171, No. 2,895,826,
3,253,924, 3,311,476, 3,458,315, 3,4
76,563, 3,591,383, 3,737,316, 3,758,30
No. 8, No. 3,767,411, No. 3,790,384, No. 3,880,661,
3,926,634, 4,004,929, 4,009,035, 4,0
12,258, 4,052,212, 4,124,396, 4,134,76
No. 6, No. 4,138,258, No. 4,146,396, No. 4,149,886,
4,178,183, 4,205,990, 4,254,212, 4,2
64,722, 4,288,532, 4,296,199, 4,296,20
0, 4,299,914, 4,333,999, 4,334,011,
No. 4,386,155, No. 4,401,752, No. 4,427,767, etc.

〔Example〕

 Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver and a blue-sensitive silver halide are provided on the antihalation layer and the gelatin layer. An emulsion layer and a protective layer were sequentially applied so that the total amount of silver was 60 mg per 100 cm ² .

The above emulsion layer is silver iodobromide in which the mol% of silver iodide is about 4.5%. In this case, the following yellow coupler (Y) is added to the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer is added. The following magenta coupler (M) was used, and the following cyan coupler (C) was used for the red-sensitive silver halide emulsion layer.

In addition, ordinary additives such as a high boiling point solvent, a sensitizing dye, a hardener and a spreading agent were appropriately used. Each of the color negative films thus obtained was imagewise exposed by a conventional method,
Negative film processor NPS-FP34 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used as a modified automatic developing machine and continuously processed under the following developing processing conditions.

From anhydrous washing stable (second tank) to anhydrous washing stable (first tank),
Counter current method (two-stage countercurrent) is used, and bleach-fixing is also performed from bleach-fixing (second tank) to bleach-fixing (first).
The counter current method to the tank) was adopted.

The amount of the treatment liquid carried in from the previous tank of each tank was 0.6 ml / dm ² .

The formulation of the tank liquid and each replenishing liquid is shown below.

Color development tank liquid: Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.0g Hydroxyethyliminodiacetic acid 3.0g Magnesium chloride 0.3g Potassium bromide 1.2 g sodium hydroxide 3.4 g N-ethylene-N-β-hydroxyethyl-3-methyl-4-aminoaniline hydrochloride 4.6 g Water was added to make 1 and the pH was adjusted to 10.1 with sodium hydroxide.

Color development replenisher: potassium carbonate 40g sodium sulfite 3.0g hydroxylamine sulfate 3.0g diethylenetriaminepentaacetic acid 3.0g potassium bromide 0.9g sodium hydroxide 3.4g N-ethylene-N-β-hydroxyethyl-3-methyl-4- Aminoaniline hydrochloride 5.6 g Water was added to adjust to 1 and the pH was adjusted to 10.2 with sodium hydroxide.

Bleach-fixing tank solution and replenisher: Diethylenetriaminepentaacetic acid Ferric ammonium salt 0.5 mol Hydroxyethyliminodiacetic acid 20 g Ammonium thiosulfate (70% wt / Vol) 250 ml Ammonium sulfite 15 g 2-Amino-5-mercapto-1,3,4 -Thiadiazole 1.0 g Ammonia water (28%) 20 ml Water was adjusted to 1 and the pH was adjusted to 7.6 with acetic acid and ammonia water.

Anhydrous washing stability tank liquid and replenisher: 5-chloro-2-methyl-4-isothiazolin-3-one 0.01 g 2-Methyl-4-isothiazolin-3-one ethylene glycol 2.0 g Finish to 1 with water, ammonia and sulfuric acid Adjust to pH 7.0 with stable tank liquid and replenisher: formalin (37% aqueous solution) 3 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7 ml Add water to finish to 1.

It is preferable that the amount of residual silver is small, but if the amount is 5 mg / dm ² or less, it has no effect on printing on photographic paper.

For this reason, 5 mg / dm ² is at a level that does not cause a problem, and the residual amount of 5 mg / dm ² or more is worse as the amount is larger. Also,
The smaller the restoration width, the better.

Under the above processing conditions, each processing time of bleach-fixing (1) and (2) in the bleach-fixing step was 5 as shown in Table 1.
As in (Experiment No. 1 to No. 5), continuous processing was carried out until the total amount of replenishment to the bleach-fix bath was 3 times the total tank volume of the bleach-fix bath.

The silver concentration of the bleach-fixing solution after this continuous processing was measured.

Next, the imagewise exposed light-sensitive material was processed in the same manner using the continuously processed bleach-fixing solution, and the amount of residual silver was measured.
Also, regarding the maximum color reversion property of the cyan dye, for these treated samples, 2% aqueous solution of red blood salt was used.
Before and after the minute treatment, the cyan density was measured with red light of an optical densitometer (PDA-65A, manufactured by Konishi Rokusha Kogyo Co., Ltd.), and the density width for recoloring (recoloring width) was measured.

The results are shown in Table-1.

As is clear from Table 1, in the bleach-fixing process consisting of two bleach-fixing baths replenished by the counter current method, the bleach-fixing time until the photosensitive material is put into the final bath is 55% of the total bleach-fixing time. If the silver concentration in the final bath is set to be less than half of the silver concentration in the first bath, the residual silver amount in the light-sensitive material is sufficiently small compared with the same bleach-fixing time and the same replenishment amount, and the cyan dye recovery Color property is improved.

Example 2 In order to change the silver concentration in the first and second tanks of the bleach-fixing baths of Experiment No. 1 and No. 4 of Example 1, the bleach-fixing tank solution was provided with 6% of the color developer in the first tank. 0.4% was mixed in the second tank, and silver bromide was added so that the silver concentration was as shown in Table 2.

Then, in the same manner as in Example 1, Table 2 shows the results of examining the residual silver amount and the recoloring width of the cyan dye.

As is clear from Table-2, in the bleach-fixing process consisting of multiple bleach-fixing baths replenished by the counter current method, the bleach-fixing time until the light-sensitive material is put into the final tank is 55% or more of the total bleach-fixing time. When the silver concentration in the final bath is set to 1/2 or less of the silver concentration in the first bath, the residual silver amount in the light-sensitive material is sufficiently good, and the cyan dye recoloration width is remarkably improved.

Example 3 The ratio of the bleach-fixing time in the first tank and the second tank was kept constant at 3: 2, the total bleach-fixing time was set to the time when the residual silver amount was 5 mg / dm ² or less, and the bleaching in the bleach-fixing solution was carried out. The type and concentration of the agent and the pH of the bleach-fix solution are changed as shown in Table-3, and the silver concentration is adjusted to the first tank.
The same experiment as in Example 2 was carried out except that the amount was 8.0 g / l and the second tank was 2.0 g / l.

The results are shown in Table-3.

From Table 3, the concentration of the ferric aminopolycarboxylic acid ferric salt in the bleach-fixing solution according to the present invention is preferably 0.25 mol / l or more,
It can be seen that the range of 0.3 to 0.8 mol / l is particularly preferable.

Example 4 For the combination shown in Table 5 of the conditions (A, B and C) of the bleach-fixing step shown in Table 4 below, the bleaching agent shown in Table 5 and its concentration, and the pH of the bleach-fixing solution, The bleach-fixing time when the residual silver amount was 5 mg / dm ² or less and the cyan dye restoration width was 0.10 or less was determined.

The results are shown in Table-5. The other conditions were the same as in Example-1.

From Table-5, when EDTAFe is used as the bleaching agent in the present invention, the pH is in the range of 4.5 to 6.5, and when DTPAFe is used, the pH is
It can be seen that the range of 6.0 to 8.0 is preferable.

The same experiment was conducted with propylenediaminetetraacetic acid, diaminopropanetetraacetic acid, cyclohexanediaminetetraacetic acid and glycol etherdiaminetetraacetic acid. As a result, it showed the same pH dependence as EDTAFeNH ₄ .

Example 5 The same experiment as Experiment No. 1 and No. 4 of Example 1 was conducted except that the bleaching accelerator and the silver concentration were as shown in Table 6 below.

The bleaching accelerator was added to both the first tank and the second tank.

The results are shown in Table-6.

Table 6 shows that it is preferable to add a bleaching accelerator to the bleach-fixing solution according to the present invention.

Example 6 Under the conditions of "no bleaching accelerator" of Example 5, except that the bleach-fixing solution was added with the following bleaching accelerators (3) to (9) respectively.
When seven kinds of experiments were carried out with 0 g / l added, the desilvering rate was high, and very favorable results were obtained.

Bleach accelerator (3) Bleach accelerator (4) Bleach accelerator (5) Bleach accelerator (6) Bleach accelerator (7) Bleach accelerator (8) Bleach accelerator (9) [Effect of the Invention] According to the present invention, in the bleach-fixing step in the processing of a light-sensitive material, sufficient desilvering can be carried out by a rapid processing, and the color returning property of a cyan dye is improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-91952 (JP, A)

Claims (1)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material after color development with a bleach-fixing solution of a multi-tank countercurrent system, wherein the bleach-fixing time until the final tank of the bleach-fixing tank is set 55% or more of the time, and the silver concentration of the final bleach-fixing tank is 1 / th of the first bleach-fixing tank.
A method of processing a silver halide color photographic light-sensitive material, which is 2 or less.