JP3041739B2 - Processing solution having bleaching ability for silver halide color photographic light-sensitive materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution having a bleaching ability for a silver halide color photographic light-sensitive material, and more particularly to a halogen solution having excellent biodegradability, low bleaching fog and excellent desilvering properties. The present invention relates to a processing solution having a bleaching ability for silver halide color photographic light-sensitive materials.

[0002]

BACKGROUND OF THE INVENTION Generally, silver halide color photographic light-sensitive materials are processed with a color developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution, a stabilizing solution and the like. Among these processing solutions, bleaching agents for bleaching silver are added to the bleaching solution and the bleach-fixing solution, and are currently most commonly used for color paper processing, color negative film processing, and the like. Is a ferric ethylenediaminetetraacetic acid complex salt. However, ferric ethylenediaminetetraacetic acid complex is not biodegradable (Biodegrada
abilities) are poor, and if spilled into rivers and soil, they would accumulate without being decomposed or would drift for a long time, which is not desirable from the standpoint of global environmental protection. Also,
As a bleaching agent that has recently been used, for example, JP-A-2-03041
, JP-A-2-103040, JP-A-63-250651, ferric salt of 1,3-propanediaminetetraacetic acid (PD
TA / Fe). This PDTA.Fe is a compound having excellent silver bleaching ability, suitable for rapid processing, and excellent in biodegradability, but has drawbacks in practical use. That is, when bleaching is performed immediately after color development, bleaching fog is generated. To solve this problem, a technique of lowering the pH using acetic acid or the like is considered, but in such a case, odor is a problem. turn into.

Another problem with PDTA / Fe is that when it is processed with a fixing solution after a bleaching solution using PDTA / Fe, or when it is used as a bleaching agent for a bleach-fixing solution, it has a strong oxidizing power. The point is that thiosulfate as a fixing agent is decomposed and sulfuration occurs.

[0004] Another bleaching agent is disclosed in JP-A-61-118.
No. 752, JP 61-50145, JP 61-50150, JP 6
A ferric diethylenetriaminepentaacetic acid complex described in, for example, the specification of JP-A-1-50147 is known, but it still has disadvantages.

[0005] That is, when the color paper is treated with the bleaching agent, a yellow stain occurs at an edge portion. This is particularly noticeable when low replenishment processing is performed, and is a problem that cannot be ignored.

[0006]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to firstly provide a processing solution having a bleaching ability for a silver halide color photographic light-sensitive material capable of rapid processing without generating bleaching fog. The second object is to provide a processing solution having a bleaching ability for silver halide color photographic light-sensitive materials having excellent biodegradability and being environmentally friendly. A third object is to provide a processing solution having a bleaching ability for a silver halide color photographic light-sensitive material, which enables stable processing without sulfuration. A fourth object of the present invention is to provide a processing solution having a bleaching ability for a silver halide color photographic light-sensitive material in which yellow contamination at the edge of the light-sensitive material is improved.

[0007] This and other objects will become apparent in the following specification.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have reached the present invention.

That is, the object of the present invention is achieved by the following processing solutions (1), (2) and (3).

(1) A processing solution having a bleaching ability for a silver halide color photographic light-sensitive material, comprising a ferric complex salt of a compound represented by the following general formula [I]:

[0011]

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In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents a hydrogen atom, a hydroxyl group, -COO
M, -PO ₃ M _2, represents a -CH ₂ COOM, -CH ₂ OH or a lower alkyl group. Provided that at least one of A ₁ , A ₂ , A ₃ and A ₄ is
-CH ₂ COOM, a -COOM or -PO ₃ M _2. M, M ₁ and M
₂ represents a hydrogen atom, an ammonium group, a sodium atom, a potassium atom, a lithium atom, or an organic ammonium group, respectively. B represents a hydrogen atom or a hydroxyl group.

(2) The bleaching ability for a silver halide color photographic light-sensitive material as described in (1) above, wherein the ratio of ammonium ions to all cations in the processing solution is 50 mol% or less. Processing solution.

(3) The silver halide color photographic material as described in (1) or (2) above, wherein the processing solution contains a compound represented by the following general formula [II] or hydroxyacetic acid. A processing solution having bleaching ability.

Formula (II) A- (COOM ¹ ) n In the formula, n is an integer of 2 to 5, and A represents a single bond or an n-valent organic group. M ¹ represents a hydrogen atom, an alkali metal atom or an ammonium group. n number of M ¹ may be the same or different.

Hereinafter, the present invention will be described in detail.

In the general formula [I], A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents a hydrogen atom,
A hydroxyl _{group, -COOM, -PO 3 M 2,} -CH 2 COOM, -CH 2 OH or a lower alkyl group (a methyl group, an ethyl group, an isopropyl group, n- propyl group etc.). However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is —CH ₂ COOM, —COOM or —PO ₃ M ₂ .
M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, a sodium atom, a potassium atom, a lithium atom or an organic ammonium group (for example, a trimethylammonium group, a triethanolammonium group, etc.). B represents a hydrogen atom or a hydroxyl group.

Preferred specific examples of the compound represented by the formula [I] are shown below.

[0019]

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[0020]

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[0021]

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[0022]

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The compounds represented by the general formula (I) are described in JP-A-63-267750, JP-A-63-267751, JP-A-2-115172,
It can be synthesized by a general synthesis method described in JP-A-2-295954 and JP-A-3-56456.

"Processing solution having bleaching ability" according to the present invention
Specifically, it means a bleaching solution, a bleach-fixing solution, and a single-bath developing bleach-fixing solution.

The second compound of the compound represented by the general formula [I]
The addition amount of the iron complex salt is 0.05 to 1 liter of the bleaching solution or the bleach-fixing solution.
The content is preferably in the range of 2.0 to 2.0 mol, more preferably 0.1 to 1.5 mol.

The compound represented by the above general formula [I] and the second compound
The molar ratio of iron ions is preferably in the range from 1: 1 to 1: 3, more preferably in the range from 1: 1.1 to 1: 2.5.

In the bleaching solution or the bleach-fixing solution of the present invention, as a bleaching agent, besides the iron complex salt of the compound represented by the above general formula [I], a ferric complex salt of the following compound can be used.

[A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycine [A'-4] ethylenediaminetetrakismethylenephosphonic acid [A '-5] Nitrilotrismethylene phosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediamine diorthohydroxyphenylacetic acid [A'-9] Hydroxyethyl Ethylenediaminetriacetic acid [A'-10] Ethylenediaminepropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15] triethylenetetramine hexaacetic acid [ In '-16] ethylenediaminetetraacetic propionic acid [A'-17] 1,3-propylene diamine tetraacetic acid [A'-18] glycol ether diaminetetraacetic acid present invention, the bleaching solution, the bleach-fixing solution and fixing solution,
JP-A-64-295258 describes imidazole and derivatives thereof or compounds represented by the general formulas (I) to (IX) described in the specification and at least one of these exemplified compounds to achieve rapidity. Can be effective against

In addition to the above-mentioned accelerators, exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and pages 22 to 25 of JP-A-63-17445. And the compounds described in JP-A-53-95630 and JP-A-53-28426 can be used in the same manner.

The temperature of the bleaching solution or bleach-fixing solution is preferably from 20 to 50 ° C., but is preferably from 25 to 45 ° C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less. The pH of the bleach-fix solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5.
It is. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing tank when processing the silver halide light-sensitive material, and can be clearly distinguished from the pH of a so-called replenisher.

In addition to the above, the bleaching solution or the bleach-fixing solution may contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various optical brighteners, an antifoaming agent or a surfactant. it can.

A preferable replenishing amount of the bleaching solution or the bleach-fixing solution is 500 ml or less, more preferably 10 to 400 ml, most preferably 20 to 350 ml per m ^{2 of the} silver halide color photographic light-sensitive material. , The effect of the present invention becomes more remarkable.

In the present invention, air or oxygen may be blown in the processing bath and in the processing replenisher storage tank, if desired, in order to increase the activity of the bleaching solution or bleach-fixing solution. Agents such as hydrogen peroxide,
Bromates, persulfates and the like may be appropriately added.

As a fixing agent used in the fixing solution or the bleach-fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of the thiocyanate is preferably at least 0.1 mol / l or more, and more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when a color negative film is processed. The thiosulfate content is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when a color negative film is processed.

In the present invention, the object of the present invention can be more effectively achieved by using a combination of a thiocyanate and a thiosulfate.

The fixing solution or the bleach-fixing solution according to the present invention may contain, alone or in combination of these fixing agents, pH buffers comprising various salts. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like.

Compounds known to be added to ordinary fixing solutions or bleach-fixing solutions, such as alkylamines and polyethylene oxides, can be added as appropriate.

Silver may be recovered from the bleach-fix solution according to the present invention by a known method.

The fixing solution or the bleach-fixing solution is described in JP-A-64-295.
It is preferable to add a compound represented by the following general formula [FA] described on page 56 of specification 258 and this exemplified compound, which not only exerts the effects of the present invention better, but also allows a small amount of photosensitive material to be used for a long time. Another effect is that the amount of sludge generated in the processing solution having a fixing ability when processing over a long period is extremely small.

[0041]

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The compound represented by the general formula [FA] described in the same specification is disclosed in US Pat. No. 3,335,161 and US Pat.
It can be synthesized by a general method as described in Japanese Patent No. 0,718. These compounds represented by the general formula [FA] may be used alone or in combination of two or more.

Good results can be obtained when the amount of the compound represented by the general formula [FA] is in the range of 0.1 to 200 g per liter of the processing solution.

The processing time with the bleaching solution and the fixing solution is optional, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 2 minutes and 20 seconds, and particularly preferably 20 seconds to 1 minute.
The range is 20 seconds. The processing time with the bleach-fix solution is 4
Minutes or less, and more preferably in the range of 10 seconds to 2 minutes and 20 seconds.

In practicing the present invention, when the ratio of ammonium ions to all cations in the processing solution having the bleaching ability of the present invention is 50 mol% or less, the effect of the present invention is more favorable. And the ratio is more preferably
It is at most 30 mol%, most preferably at most 10 mol%.

The nitrate according to the present invention is specifically sodium nitrate, ammonium nitrate, potassium nitrate,
Lithium nitrate and the like.

Next, the compound represented by formula (II) will be described in detail.

In the general formula [II], the n-valent organic group represented by A includes an alkylene group (for example, a methylene group,
Ethylene, trimethylene, tetramethylene, etc.),
Alkenylene group (eg ethenylene group etc.), alkynylene group (eg ethinylene group etc.), cycloalkylene group (eg 1,4-cyclohexanediyl group etc.), arylene group (eg o-phenylene group, p-phenylene group etc.), alkane Examples thereof include a triyl group (eg, a 1,2,3-propanetriyl group) and an arenetriyl group (eg, a 1,2,4-benzenetriyl group).

The n-valent group represented by A is a substituent (for example, a hydroxy group, an alkyl group, a halogen atom, etc.)
(E.g., 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, chloro Ethenylene). Preferred specific examples of the compound represented by the general formula [II] are shown below.

[0050]

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[0051]

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Of the above exemplified compounds, particularly preferred are the exemplified compounds (II-1), (II-3), (II-4) and (II-
5), (II-6), (II-16) and (II-18), and particularly preferably (II-5).

The compound represented by the general formula [II] is preferably contained in an amount of 0.05 to 2.0 mol per liter of a processing solution having a bleaching ability, more preferably 0.2 to 1.0 mol.

[0054]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples of the present invention, but the present invention is not limited to these Examples.

Example 1 Preparation of a color photographic light-sensitive material (color paper) A paper support is shown below on a support in which polyethylene is laminated on one side and polyethylene containing titanium oxide is laminated on the first layer side on the other side. Each layer of the constitution was applied to prepare a multilayer color photographic light-sensitive material. The coating solution was prepared as described below.

First layer coating solution 26.7 g of yellow coupler (Y-1), 100 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), additive (H
Q-1) 0.67 g was dissolved in 6.67 g of a high boiling point solvent (DNP) by adding 60 ml of ethyl acetate, and this solution was dissolved in a 20% surfactant (S
U-1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% aqueous gelatin solution containing 7 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardener, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

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[0062]

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[0063]

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[0064]

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[Method of Preparing Blue-Sensitive Silver Halide Emulsion]
(A) in 1000 ml of a 2% aqueous gelatin solution kept at
Solution) and (solution B) with pAg = 6.5 and pH = 3.0.
Add simultaneously over 0 minutes, and further add the following (Solution C) and (Solution D)
Was added simultaneously over 180 minutes while controlling the pH to 7.3 and the pH to 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Add 10 g of silver nitrate water and 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water 600 ml (D solution) Silver nitrate 300g Water was added and after the addition of 600ml, desalting was performed using 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. A monodispersed cubic emulsion EMP-1 having a diameter of 0.85 µm, a coefficient of variation in particle size distribution of 7%, and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-A).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / Mol AgXX (BS-2) 1 × 10 ⁻⁴ mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] (solution A) and (B
Liquid) and the addition time of (Liquid C) and (Liquid D) in the same manner as EMP-1, except that the average particle diameter was 0.43 μm.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
To obtain a monodispersed cubic emulsion EMP-2.

The following compounds were used for EMP-2.
Chemical ripening was performed at 120 DEG C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 4 × 10 ⁻⁴ mol / Mol AgX [Method of preparing red-sensitive silver halide emulsion] (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle size was 0.50 μm.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
Was obtained as a monodispersed cubic emulsion EMP-3.

The following compounds were used for EMP-3.
At 90 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (E
m-C).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol Ag
X stabilizer (STAB-1) 6 × 10 ^-4 mol / mol AgX sensitizing dye (RS-1) 4 × 10 ^-4 mol / mol AgX

[0074]

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The color photographic light-sensitive material (color paper) was exposed according to a conventional method, and then processed using the following processing steps and processing solutions.

Processing step Processing temperature Processing time Replenishment amount (1) Color development 39.0 ± 0.3 ° C. 27 seconds 70 ml / m ² (2) Bleaching and fixing 37.5 ± 0.5 ° C. 27 seconds 55 ml / m ² (3) Stable (three-cascade) 30-34 ° C 90 seconds 248ml / m ² (4) Drying 60-80 ° C 30 seconds Color developer Triethanolamine 10g Diethylene glycol 6g N, N-diethylhydroxylamine 3.6g Hydrazinodiacetic acid 5.0g Potassium bromide 20mg Potassium chloride 3.5 g Diethylenetriaminepentaacetic acid 5g Potassium sulfite 0.3g Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 5.5g Potassium carbonate 25g Potassium hydrogen carbonate 5g Water To make the total volume 1 liter, and the pH is adjusted to 10.10 with potassium hydroxide or sulfuric acid. Replenisher for color development Triethanolamine 14.0 g Diethylene glycol 8.0 g N, N-diethylhydroxylamine 5 g Hydrazinodiacetic acid 7.5 g Potassium bromide 2
mg potassium chloride 2.5
g Diethylenetriaminepentaacetic acid 7.5 g Potassium sulfite 0.5 g Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate) 8 g Potassium carbonate 30 g Potassium hydrogen carbonate 1 g Water In addition, the total volume is adjusted to 1 l and the pH is adjusted to 10.40 with potassium hydroxide or sulfuric acid. Bleaching-fixing solution Water 600 ml Ferric complex salt of organic acid (described in Tables 3 and 4) 0.15 mol Thiosulfate 0.6 mol Sulfite 0.15 mol Exemplified compound II-57 g pH 7.0 using ammonia water, potassium hydroxide and acetic acid as appropriate. Set to 0 and finish to 1 liter.

However, as shown in Tables 3 and 4, in order to adjust the ratio (mol%) of the ammonium ion in the bleach-fix solution, the above-mentioned ammonium salt and potassium salt of the additives were appropriately used.

Bleach-fix replenisher: The concentration of each additive in the bleach-fix was increased by a factor of 1.75, and p
H was used at 5.8. Stabilizing replenisher ortho-phenyl phenol 0.1g Uvitex MST (manufactured by Ciba _{Geigy) 1.0g ZnSO 4 · 7H 2 O} 0.1g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid (60 % Solution) 3.
0 g ethylenediaminetetraacetic acid 1.5
g. Adjust the pH to 7.8 with aqueous ammonia or sulfuric acid and adjust to 1 liter with water.

A running process was performed using the prepared color paper and the processing solution.

In the running process, the automatic developing machine is filled with the above-described color developing tank solution, filled with the bleach-fixing tank solution and the stabilizing tank solution, and replenished with the above-described color developing solution every three minutes while processing the color photographic light-sensitive material. The solution, the bleach-fix replenisher and the stable replenisher were replenished through a metering pump.

In the running process, continuous processing was carried out until the amount of the bleach-fix tank solution replenished in the bleach-fix tank solution became three times the volume of the bleach-fix tank solution. Note that 1R means that the bleach-fix replenisher for the capacity of the bleach-fix tank is replenished.

After the treatment, the amount of fluorescent X-ray residual silver in the exposed area of the color paper was measured. Further, the state of stain on the edge of the processed color photographic light-sensitive material at the end of the running test was observed. Further, the state of the bleach-fixing tank liquid (production of sulfide) at the end of the running was visually evaluated. Tables 3 and 4 show these results.

In Tables 3 and 4, the meanings of the symbols in the column of the occurrence state of sulfuration are as follows.

◎ No sulfide was observed at all ○ Very little suspended matter was observed on the liquid surface △ Slight sulfide generation was observed × Clear sulfide generation was observed ×× A large amount of sulfide was observed Occurrence is observed.

The meanings of the symbols in the column of edge dirt are as follows.

◎ No edge stains were observed at all. エ ッ ジ Very slight edge stains were observed. Δ Slight edge stains were observed. × Edge stains were observed to be a serious problem. XX Extremely edge stains were observed.

[0087]

[Table 3]

[0088]

[Table 4]

In Tables 3 and 4, and in the following table, ED
TA ・ Fe is ferric ethylenediaminetetraacetic acid complex salt, PDTA ・ Fe
Is ferric complex salt of 1,3-propylenediaminetetraacetic acid, DTPA / Fe
Is a ferric complex of diethylenetriaminepentaacetic acid, NTA · Fe is a ferric complex of nitrilotriacetic acid, (I-1) · Fe is a ferric complex of the exemplary compound (I-1), and (I-16) · Fe is Exemplary compound (I-
16) Ferric complex salt of (I-18) .Fe is exemplified compound (I-18)
Represents a ferric complex salt of

As can be seen from Tables 3 and 4, when the ferric complex salt of the organic acid of the present invention was used, the amount of residual silver was small, the stain on the edge portion was good, and the storage stability of the bleach-fix solution was low. It turns out that it is good. Further, when the ratio of ammonium ions to all cations in the bleach-fix solution is 50 mol% or less,
It can be seen that the above effects are more favorable, especially when the content is 30 mol% or less, and the best when the content is 10 mol% or less.

[0091] In Example 2 the following examples, the amount of silver halide photographic light-sensitive material is particularly shows the number of grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver are shown in terms of silver. A silver iodobromide color photographic light-sensitive material (color film) was prepared as follows.

Silver iodobromide color photographic light-sensitive material A triacetyl cellulose film support (60 μm) is subjected to a subbing process on one side (surface), and then sandwiched between the substratum and the opposite of the subcoated surface. On the side surface (back surface), each layer having the following composition was formed sequentially from the support side.

Back surface first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Back surface second layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle diameter 0.2 μm) 50 mg On the surface of the triacetyl cellulose film support thus formed, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material.

First layer: Antihalation layer Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g 〃 (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer Gelatin 1.3 g Third layer; Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average particle size 0.3 μm) 0.4 g 〃 (Average particle size 0.4 μm) 0.3 g increase Sensitizing dye (S-1) 3.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) 〃 (S-3) 0.3 × 10 ^-4 (mol / 1 mol of silver) Cyan coupler (C-1) 0.50 g 〃 (C-2) 0.20 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g 〃 (D-2) 0.01 g high boiling solvent (Oil-1) 0.55 g gelatin 1.0g fourth layer; high-sensitivity red-sensitive emulsion layer silver iodobromide emulsion (average particle size 0.7 [mu] m) 0.9 g sensitizing dye (S-1) 1.7 × 10 -4 ( Le / mole of silver) 〃 (S-2) 1.6 × 10 -4 ( mol / 1 mol of silver) 〃 (S-3) 0.2 × 10 -4 ( mol / mole of silver) Cyan Coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.0
2g High boiling point solvent (Oil-1) 0.30
g Gelatin 1.0 g Fifth layer; Intermediate layer Gelatin 0.8 g Sixth layer; Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Average particle size 0.4 μm) 0.6 g 〃 (Average particle size 0.3 μm) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S-5) 1.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.20 g 〃 (MB) 0.40 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g 7th layer; high-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion ( (Average particle size 0.7 μm) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) 〃 (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S- 8) 0.5 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.5 g 〃 (MB) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent Oil-2) 0.35 g Gelatin 1.0g eighth layer; yellow filter layer Yellow colloidal silver 0.1g additives (HS-1) 0.0
7g〃 (HS-2) 0.0
7g {(SC-1) 0.12g High-boiling point solvent (Oil-2) 0.15g Gelatin 0.9g 9th layer; low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.3μm) 0.25g {(average grain Diameter 0.4 μm) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.71 g 〃 (Y-2) 0.30 g DIR compound (D-1) 0.003 g 〃 (D-2) 0.006 g High boiling solvent (Oil-2) 0.18 g Gelatin 1.2 g 10th layer; high-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average particle size 0.8 μm) 0.5 g sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) {(S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g} (Y-2) 0.20 g High boiling solvent (Oil-2) 0.05 g Gelatin 0.9 g 11th layer; 1st protective layer Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g 〃 (UV- 2) 0.10g Additive (HS-1) 0.2g 〃 (HS-2) 0.1 g High boiling solvent (Oil-1) 0.0
7g 〃 (Oil-3) 0.07
g Gelatin 0.85 g 12th layer; 2nd protective layer Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: ethyl methacrylate: methacrylic acid = 3: 3: 4 (weight) Ratio) (average particle size: 3 μm) 0.13 g The silver bromoiodide color photographic material described above further comprises compounds Su-1, Su-2, a viscosity modifier, a hardener H-1, H
-2, stabilizer ST-1, antifoggant AF-1, AF-
2 (weight average molecular weight of 10,000 and 1.100000),
Dyes AI-1, AI-2 and compound DI-1 (9.4 mg / m
² ) Contains.

[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[Preparation of emulsion] The silver iodobromide emulsion used in the tenth layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average particle size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

The solution <G-1> was heated at a temperature of 70 ° C., a pAg of 7.8 and a pH of
At 7.0, a seed emulsion equivalent to 0.34 mol was added with good stirring.

(Formation of Internal High Iodine Phase—Core Phase) Thereafter, while maintaining a flow ratio of <H-1> to <S-1> of 1: 1, the accelerated flow rate (the flow rate at the end is 2. Initial flow rate
(6 times) and added over 86 minutes.

(Formation of External Low Iodine Phase-Shell Phase-) Subsequently, while maintaining pAg 10.1 and pH 6.0, <H-2> and <S
-2> was added at a flow rate accelerated at a flow ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during particle formation were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the particles were formed, the particles were subjected to a water washing treatment by a conventional flocculation method, and then gelatin was added for redispersion, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a variation coefficient of grain size distribution of 12.4% and a silver iodide content of 9.0 mol%.

<G-1> Ossein gelatin 100.0 g 10% by weight methanol solution of compound-1 25.0 ml 28% ammonia aqueous solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml <H-1> ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide
6g finish with water 103
0.5ml <S-1> Silver nitrate 309.2g 28% ammonia aqueous solution equivalent Finish with water 1030.5ml <H-2> Ossein gelatin 302.1g Potassium bromide 770.0g Potassium iodide 33.2g Finish with water 3776.8ml <S-2 > Silver nitrate 1133.0g 28% aqueous ammonia solution Equivalent to water 3776.8ml Compound-1

[0112]

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In the same manner, the average grain size, temperature,
The emulsions having different average grain sizes and different silver iodide contents were prepared by changing pAg, pH, flow rate, addition time and halide composition.

All were core / shell type monodisperse emulsions having a variation coefficient of particle size distribution of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. , 1-phenyl-5-mercaptotetrazole.

The silver bromoiodide color photographic material was prepared so that the average silver iodide content was 8 mol%.

The photosensitive material thus prepared was exposed to wedges according to a conventional method, and then subjected to running processing according to the following processing steps. However, the running process is continued until 2 times the capacity of the bleach-fix tank is replenished (2R).
Performed continuously.

Processing step Processing time Processing temperature Replenishment amount (per 135 size 24EX) (1) Color development 3 minutes 15 seconds 38 ° C 20 ml (2) Bleaching and fixing 3 minutes 15 seconds 38 ° C 30 ml (3) Stabilization 1 minute 38 ℃ 40ml (3-tank cascade) (4) Drying 1 minute 40-80 ℃ Color developing solution Potassium carbonate 30.0g Sodium hydrogen carbonate 2.5g Potassium sulfite 3.0g Sodium bromide 1.3g Potassium iodide 1.2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 l, add potassium hydroxide or Adjust the pH to 10.00 with 20% sulfuric acid.

Color developing replenisher potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.5 g hydroxylamine sulfate 3.5 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate Salt 6.0 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and adjust to pH 10.12 using potassium hydroxide or 20% sulfuric acid.

Bleach-fixing tank solution Water 600 ml Ferric complex salt of organic acid (described in Tables 5 and 6) 0.4 mol Thiosulfate 2.0 mol Sulfite 0.15 mol Exemplified compound II-5 2 g Adjusted to pH 7.0 using aqueous ammonia and acetic acid Adjust and finish to 1 liter.

However, as shown in Tables 5 and 6, in order to adjust the ratio (mol%) of the ammonium ion in the bleach-fix solution, the above-mentioned ammonium salt and potassium salt of the additives were appropriately used.

Bleach-fix replenisher The above-mentioned bleach-fix tank solution was used at a concentration of 1.07 times and a pH of 6.0. Stabilizing solution (tank solution and replenisher) o-phenylphenol 0.5 g hexamethylenetetramine 5.0 g diethylene glycol 10 g

[0122]

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Adjust the pH to 8.0 with KOH, add water and add 1
Finish to l.

A running process similar to that of the first embodiment is performed.
The amount of residual silver after processing and the state of sulfidation of the bleach-fix solution were evaluated.

The results are summarized in Tables 5 and 6.

[0126]

[Table 5]

[0127]

[Table 6]

From Tables 5 and 6, it can be seen that when the ferric complex salt of an organic acid of the present invention was used, the amount of residual silver was small and the storage stability of the bleach-fix solution was good. Further, when the ratio of ammonium ions to all cations in the bleach-fix solution is 50 mol% or less, the above effect is more favorable,
It can be seen that particularly good results are obtained when the content is 30 mol% or less, and the best results are obtained when the content is 10 mol% or less.

Example 3 Example 2 was repeated except that the processing steps were changed as follows, and that the bleaching solution and the fixing solution were changed to processing solutions having the following compositions.
The same experiment was performed. (The number of processing rounds per day was 0.05R (for bleaching solution).) Processing step Processing time Processing temperature Replenishment amount (per 135 size 24EX) (1) Color development (1 tank) 3 minutes 15 seconds 38 ° C 20ml (2) Bleaching (〃) 45 seconds 38 ° C 5 ml (3) Settling (〃) 1 minute 30 seconds 38 ° C 33 ml (4) Stabilization (3 tank cascade) 1 minute 38 ° C 40 ml (5) Drying (40) 1 min Bleaching tank liquid Water 600 ml Ferric acid complex salt of organic acid (Table 7 and Table 8) 0.35 mol Ethylenediaminetetraacetic acid 10 g Bromide salt 1.3 mol Glacial acetic acid 0.8 mol Adjust the pH to 4.5 with ammonia water and acetic acid. Add water to make up to 1 liter.

However, as shown in Tables 7 and 8, in order to adjust the ratio (mol%) of ammonium ions in the bleach-fix solution, the ammonium salt and potassium salt of the above additives were appropriately used.

Bleach replenisher The concentration of each additive in the bleach tank solution was adjusted to 1.2 times,
Was used as 3.5.

Fixer (Tank solution and replenisher) Ammonium thiosulfate (70% solution) 350 ml Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetate 0.5 g Water was added to make 1 liter, and acetic acid and aqueous ammonia were added. And adjust to pH 6.5.

After the continuous processing, the magenta transmission density (green light density) of the unexposed portion of the film sample was measured, and at the same time, the amount of residual silver in the exposed portion was measured by a fluorescent X-ray method.

The above results are summarized in Tables 7 and 8.

[0135]

[Table 7]

[0136]

[Table 8]

From Tables 7 and 8, it can be seen that when the ferric complex salt of the organic acid of the present invention was used, the amount of residual silver was small, and the increase in the magenta transmission density in the unexposed area was small. Further, when the ratio of ammonium ion to all cations in the bleaching solution is 50 mol% or less, the above effect is more favorable, and when the ratio is 30 mol% or less, the effect is particularly good. You can see that there is.

Example 4 Using the same sample as in Example 1, the processing was performed by changing the processing steps and the processing liquid as follows.

Processing step Processing temperature Processing time Replenishment amount (1) Color development 39.0 ± 0.3 ° C. 20 seconds 55 ml / m ² (2) Bleaching 37.5 ± 0.5 ° C. 15 seconds 30 ml / m ² (3) Fixing 37.5 ± 0.5 ° C. 15 seconds 55 ml / m ² (4) Stable (3 tank cascade) 30-34 ° C 90 seconds 248 ml / m ² (5) Drying 60-80 ° C 30 seconds Color developing solution: same as in Example 1 Color developing replenisher: Example 1 The same bleaching solution Ferric organic acid complex salt (described in Table 9) 0.1 mol Bromide salt 60 g Acetic acid 0.4 mol Water was added to 1 l, and the pH was adjusted to 4.5 with an aqueous potassium carbonate solution.

However, as shown in Tables 9 and 10, in order to adjust the ratio (mol%) of ammonium ions in the bleaching solution, ammonium salts and potassium salts of the above additives were appropriately used.

Bleach replenisher The concentration of each additive in the above bleach was doubled and the pH was set to 3.0.

Fixer and Fixer Replenisher Ammonium Thiosulfate 250 g Sodium Metabisulfite 20 g Ethylenediaminetetraacetic acid
0.8 g of water was added to make 1 liter, and the pH was adjusted to 6.5 with acetic acid and aqueous ammonia.

Stabilizing Solution and Stable Replenishing Solution Same as in Example 1 The same evaluation as in Example 1 was performed. The results are shown in Tables 9 and 10.

[0144]

[Table 9]

[0145]

[Table 10]

As can be seen from Tables 9 and 10, when the ferric complex salt of an organic acid of the present invention was used, the amount of residual silver was small, the stain on the edge portion was good, and the preservability of the bleaching solution was good. It turns out that it is. Further, when the ratio of ammonium ion to all cations in the bleaching solution is 50 mol% or less, the above effect is more favorable, and when the ratio is 30 mol% or less, the effect is particularly good. You can see that.

Example 5 The same procedure as in Example 3 was carried out except that the acetic acid in the bleaching solution used in Experiment No. 3-30 of Example 3 was changed to the same molar amount of an organic acid or an inorganic acid shown in Table 10 below. The experiment was performed. Table 11 shows the results.

[0148]

[Table 11]

From the above Table 11, it can be seen that, when the compound represented by the general formula [II] or hydroxyacetic acid is used in combination in the treatment solution of the present invention, there is no odor, and the effect of the present invention is less. It turns out that it plays better.

Example 6 The procedure of Example 4 was repeated, except that the acetic acid in the bleaching liquor used in Experiment No. 4-18 of Example 4 was changed to the same molar amount of an organic or inorganic acid shown in Table 12 below. Was conducted. Table 12 shows the results.

[0151]

[Table 12]

From the above Table 12, it can be seen that when the compound represented by the general formula [II] is used in combination in the treatment solution of the present invention, the intended effects of the present invention are more favorably exhibited.

Example 7 Chelating agents generally known to be used for photography, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), and an exemplary compound ( I−
1), (I-2), (I-3), (I-16), (I-17), (I-18) and (I-20) ferric complex salts were tested for OECD chemicals. Guideline 301C revised MITI test (I) (May 12, 1981)
The biodegradation was determined according to the following formula:

As a result, the iron complex salt of the chelating agent of the present invention has extremely good biodegradability, whereas EDTA, DTPA
Further, the iron complex salt of HEDTA hardly decomposed, and it was found that the chelating agent of the present invention was extremely preferable from the viewpoint of protecting the global environment.

Example 8 The ferric salt of an organic acid to be used was prepared in accordance with the exemplified compound (I-
2) The same experiment as in Example 3 was carried out except that (I-10), (I-19), (I-20), (I-21) and (I-22) were changed. In the case of using the organic acid ferric complex salt of the present invention, it was confirmed that the amount of residual silver was small and the increase in the magenta transmission density in the unexposed portion was small, as in Example 3.

[0156]

According to the present invention, rapid processing can be performed without bleaching fog, and biodegradability is excellent.
Provided is a processing solution which has environmental suitability, enables stable processing without sulfuration, and has a bleaching ability for a silver halide color photographic light-sensitive material in which yellow contamination generated at the edge of the light-sensitive material is improved.

Claims (3)

(57) [Claims] 1. A processing solution having a bleaching ability for a silver halide color photographic light-sensitive material, characterized by containing at least a ferric complex salt of a compound represented by the following general formula [I]. Embedded image [Wherein A ₁ , A ₂ , A ₃ and A ₄ may be the same or different, and each represents a hydrogen atom, a hydroxyl group, -COOM, -PO
₃ M ₂ , —CH ₂ COOM, —CH ₂ OH or a lower alkyl group. However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is -CH ₂ CO
OM, a -COOM or -PO ₃ M _2. M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, a sodium atom, a potassium atom, a lithium atom or an organic ammonium group. B represents a hydrogen atom or a hydroxyl group. ] 2. A processing solution having a bleaching ability for a silver halide color photographic light-sensitive material according to claim 1, wherein the ratio of ammonium ions to all cations in the processing solution is 50 mol% or less. . 3. The bleaching ability for a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution contains a compound represented by the following general formula [II] or hydroxyacetic acid. Processing solution. General formula [II] A- (COOM ¹ ) n [wherein, n is an integer of 2 to 5, and A represents a single bond or an n-valent organic group. M ¹ represents a hydrogen atom, an alkali metal atom or an ammonium group. n number of M ¹ may be the same or different. ]