JP3049334B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material (hereinafter, referred to as a silver halide color photographic material).
More specifically, the processing method of "photosensitive material") is more specifically a photosensitive material capable of rapid processing with little precipitation of bleaching solution components at a constant temperature, generation of tar during running, little precipitate (sludge). Regarding the processing method.

[Background of the Invention] Processing of a photosensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition, rinsing processing, stabilization processing, and the like are added as additional processing steps.

In a processing solution having a bleaching ability used in a desilvering step of a photographic material, an inorganic oxidizing agent such as red blood salt and dichromate has been widely used as an oxidizing agent for bleaching image silver.

However, processing solutions having bleaching ability containing these inorganic oxidizing agents have been pointed out with some serious drawbacks. For example, red blood salts and dichromates are relatively excellent in terms of the bleaching power of image silver, but may be decomposed by light to generate harmful cyan ions and hexavalent chromium ions, which cause pollution. It has unfavorable properties for prevention.
Further, the processing liquid containing these inorganic oxidizing agents has a drawback that it is difficult to recycle the processing liquid without discarding the waste liquid after the processing.

On the other hand, there are few pollution problems,
In order to meet the demands for simplification and reusability of waste liquids, treatment liquids using an organic acid metal complex such as aminopolycarboxylic acid metal complex as an oxidizing agent have come to be used. However, a processing solution using a metal complex salt of an organic acid has a drawback that the bleaching speed (oxidation speed) of image silver (metal silver) formed in the developing step is slow because of the slow oxidizing power. . For example, iron (III) ethylenediaminetetraacetate complex salt, which is considered to have strong bleaching power among aminopolycarboxylic acid metal complex salts, is partially used as a bleaching solution and a bleach-fixing solution. In a high-sensitivity silver halide color photographic light-sensitive material mainly composed of a silver iodobromide emulsion, in particular, containing silver iodide as silver halide, a color silver film for photographing with a high silver content, a color negative film for photographing, and a color reversal film, It has the disadvantage that the bleaching power is insufficient and the bleaching step requires a long time.

In order to compensate for such a drawback, it is common to increase the concentration of the aminopolycarboxylic acid ferric complex salt or increase the bromide concentration, but the aminopolycarboxylic acid ferric complex salt or bromide concentration is increased. When the concentration exceeds a certain level, bleaching tends to be suppressed, and the bleaching power is extremely insufficient. In recent years, there has been a high demand for low pollution, and low replenishment has been performed. However, when the concentration of ferric aminopolycarboxylic acid ferric complex or bromide is high, the precipitation of bleaching components easily occurs at low temperatures. In addition, there is a problem that the enrichment is limited, and as a result, it is difficult to reduce the replenishment.

When the concentration of bromide increases, so-called silver sludge, which causes a large amount of precipitates which are considered to be silver compounds in the bleaching solution, becomes a problem.

Therefore, rapidity cannot be achieved by increasing the concentration of the ferric aminocarboxylate complex or the concentration of bromide, but rather the above-mentioned problem occurs, which is a serious problem in practical use.

However, in recent years, so-called compact labs (also known as mini labs) have emerged in order to shorten the processing time of silver halide color photographic light-sensitive materials and reduce collection and delivery costs. In such labs, complicated labor and management are required. Although a low-pollution-type treatment liquid that is unnecessary and has little waste liquid is desired, it is currently insufficient. In addition, the amount of photosensitive material to be processed per day varies in minilabs.
It is 0 or more. In laboratories with high throughput, there are relatively few problems, but in minilabs with low throughput, there is concentration of bleaching solution, which may reduce bleaching power, precipitate in the tank solution, or cause tar to adhere to the tank wall. Often seen.

In recent years, however, there has been a demand for lower pollution, lower cost, etc., or the stabilization of the processing solution itself, and even a short-time processing service (1 Hour Photo) that returns to the user within a few hours from reception. Have been. Under such circumstances, the above problems are becoming more and more serious.

[Effects of the Invention] Accordingly, a first object of the present invention is to provide a method for processing a light-sensitive material in which precipitation of bleaching components at a low temperature, generation of tar during running, and generation of precipitates are small.

A second object of the present invention is to provide a method for processing a photographic material which can be processed quickly.

A third object of the present invention is to provide a processing method for a photographic material capable of obtaining stable photographic performance regardless of the processing amount of the photographic material.

[Constitution of the Invention] The processing method according to the present invention, which achieves the above object, is a processing method for a silver halide color photographic light-sensitive material in which a color developing process is immediately followed by processing with a bleaching solution, followed by processing with a processing solution having fixing ability. In the above method, the bleaching treatment contains at least one ferric complex salt of a compound represented by the following general formula [A], and the bromide concentration per bleach solution is
The bleaching solution is 0.15 mol or more and 1.00 mol or less, and the bleaching solution and the processing solution having the fixing ability are subjected to forced stirring instead of the usual diffusion movement of the solution.

General formula [A] Wherein A _{1 to} A ₄ may be the same or different, and
₂ OH, represents a -COOM or -PO ₃ M ₁ M _2. M, M ₁ and M ₂ each represent a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. [Specific Configuration of the Invention] Hereinafter, the present invention will be described.

The bleaching solution according to the present invention contains at least one selected from ferric complex salts of the compound represented by the general formula [A] (hereinafter, referred to as ferric complex salts of the present invention).

The ferric complex salt of the present invention has a stronger silver bleaching power than conventional ferric aminopolycarboxylic acid complex salts, and is a preferred compound for speeding up the bleaching bath. Further, since the silver bleaching power is strong, it is not necessary to increase the concentration of ferric salt, which has been conventionally performed for processing a silver halide emulsion containing iodide, and processing can be performed even at a low concentration. Further, there is an effect that the replenisher solution can be concentrated for low replenishment.

Next, the compound represented by the general formula [A] will be described in detail.

A _{1 to} A ₄ may be the same or different, and —CH ₂ O
H, —COOM or —PO ₃ M ₁ M ₂ is represented, and M, M ₁ and M ₂ each represent a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, propylene, butylene, pentamethylene, etc.). Examples of the substituent include a hydroxyl group. Preferred specific examples of the compound represented by the general formula [A] are shown below.

As the compounds of (A-1) to (A-8), in addition to the above, their sodium salts, potassium salts or ammonium salts can be arbitrarily used. From the viewpoint of the effects of the present invention, ammonium salts of these ferric complex salts are preferably used.

Among the above-mentioned compound examples, those particularly preferably used in the present invention include (A-1), (A-2) and (A-
4) and (A-7), and particularly preferred is (A-1).

The ferric complex salt of the compound represented by the general formula [A] is preferably used in a range of 0.002 mol to 0.4 mol, more preferably 0.01 mol to 0.3 mol, particularly preferably 0.05 mol to 0.25 mol per bleaching solution. Range.

In the bleaching solution of the present invention, a ferric complex salt of the compound represented by the above general formula [A] may be added to a ferric complex salt of another aminopolycarboxylic acid (for example, a ferric complex salt of ethylenediaminetetraacetic acid, a diethylenetriaminepentaacetic acid salt). Diiron complex salt, 1,2-cyclohexanediaminetetraacetic acid ferric complex salt, glycol ether diaminetetraacetic acid ferric complex salt, etc.). In particular, it is preferable to use in combination with a ferric ethylenediaminetetraacetic acid complex salt from the viewpoint of economy and less bleaching fog.

In the bleaching solution and / or the bleach-fixing solution according to the present invention, imidazole and its derivatives or the following general formulas [I] to [I]
X], when it contains at least one compound represented by the formula (I), the effect of the object of the present invention is exhibited more favorably, and further, there is another effect of improving the precipitation caused by silver in the bleaching solution. Is more preferably used.

General formula [I] [In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocyclic ring (including a condensed 5- to 6-membered unsaturated ring), and R ₁ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 6 alkyl groups,
Represents a cycloalkyl group, an aryl group, a heterocyclic group (including those in which a 5- to 6-membered unsaturated ring is condensed), or an amino group. General formula [II] [Wherein, R ₂ and R ₃ each represent a hydrogen atom and a carbon atom 1
Represents an alkyl group, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. A is Or n ₁ valent heterocyclic residue (unsaturated ring 5-6 members including those condensed) represents, X is = S, represents a = O or = NR ". Here, R and R ′ Is the same as R ₂ and R ₃ respectively, X ′ is the same as X, Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue,
An alkyl group, or M represents a divalent metal atom, R ″ represents a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group,
Represents an aryl group, a heterocyclic residue (including a condensed 5 to 6-membered unsaturated ring) or an amino group, and n _{1 to} n ₆ and m _{1 to} m ₅ each represent an integer of 1 to 6 Represent.

B represents an alkylene group having 1 to 6 carbon atoms; Wherein R ₄ and R ₅ have the same meanings as R ₂ and R ₃ , respectively.
However R ₄ and R ₅ may each represent -B-SZ, also R ₂ and R _3, R and R ', R ₄ and R ₅ may be bonded to each other to form a ring.

 In addition, the compound represented by the formula is an ethanolated compound and
Including its salts. General formula [III][Where R₆And R₇Are hydrogen atom and carbon atom 1 respectively
To 6 alkyl groups, hydroxy groups, carboxy groups,
Group, an acyl group having 1 to 3 carbon atoms, an aryl group,
Kenyl group or -B₁-S-Z₁Represents Where R₆And R₇Is
They may combine to form a ring. Y₁Represents N- or CH-
Represents, B₁Represents an alkylene group having 1 to 6 carbon atoms;₁
Represents a hydrogen atom, an alkali metal atom, an ammonium group,
Or a nitrogen-containing heterocyclic residue orRepresents n₇Represents an integer of 1 to 6. General formula [IV][Where R₈And R₉Are eachAnd R_TenIs an alkyl group or-(CH_Two) N₈SO_Three The table
You. (However, R_TenIs-(CH_Two) N₈SO_Three , L represents 0
And represents 1 when it is an alkyl group. ) G Represents an anion
You. n₈Represents an integer of 1 to 6. General formula [V][Where Q₁Is a nitrogen-containing heterocycle (5- to 6-membered unsaturated ring or
Is necessary to form a compound having a condensed saturated ring)
Atom group, R₁₁Is a hydrogen atom, an alkali metal atom,Or an alkyl group. Where Q 'is Q₁Synonymous with
You. General formula [VI][Where D₁, D_Two, D_ThreeAnd D_FourAre each a simple bond,
Represents an alkylene group or a vinylene group having 1 to 8 carbon atoms.
Then q₁, Q_Two, Q_ThreeAnd q_FourRepresents 0, 1 or 2 respectively
You. The ring formed with the sulfur atom has an additional 5 to 6 members
May be condensed with a saturated or unsaturated ring. General formula [VII][Where X_TwoIs -COOM ', -H, -OH, -SO_ThreeM ′, − CONH_Two,
−SO_TwoNH_Two, −NH_Two, −SH, −CN, −CO_TwoR₁₆, −SO_TwoR₁₆, −OR₁₆,
NR₁₆R₁₇, −SR₁₆, −SO_ThreeR₁₆, −NHCOR₁₆, −NHSO_TwoR₁₆, −OCO
R₁₆Or -SO_TwoR₁₆And Y_TwoIs Or a hydrogen atom, m₉And n₉Are 1 to 10
Represents a number. R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇And R₁₈Are each
Hydrogen atom, lower alkyl group, acyl group orAnd R₁₆Represents a lower alkyl group; R₁₉Is -NR₂₀R
_{twenty one}, -OR_{twenty two}Or -SR_{twenty two}And R₂₀And R_{twenty one}Is water
Represents an elementary atom or a lower alkyl group;_{twenty two}Is R₁₈Combined with
Represents the group of atoms necessary to form a ring. R₂₀Or R_{twenty one}And R
₁₈And may form a ring. M 'is a hydrogen atom or
Represents a cation. General formula [VIII] In the formula, Ar is a divalent aryl group or an aryl group and oxygen
2 in combination with an atom and / or an alkylene group
Represents a valent organic group, B_TwoAnd B_ThreeIs lower alkylene
Represents a group, R_{twenty three}, R_{twenty four}, R_{twenty five}And R₂₆Is hydroxy
Represents a substituted lower alkylene group, wherein x and y are each 0 or
Represents 1. G ′ represents an anion, and z is 0, 1 or 2
Represents General formula [IX][Where R₂₉And R₃₀Are hydrogen and alkyl
Group, an aryl group or a heterocyclic group, R₃₁Is hydrogen field
Represents an atom or an alkyl group, R₃₂Is a hydrogen atom or carboxy
Represents a group. The compounds represented by the general formulas [I] to [IX] used in the present invention.
Compounds or imidazole and its derivatives are generally bleached
Compound used as an accelerator, the following of the present invention
It is called a bleach accelerator.

Typical specific examples of the bleaching accelerator of the present invention represented by the general formulas [I] to [IX] include, but are not limited to, the following.

Illustrative compounds _{(II-6) H 2 N} -CSNHNHCS-NH 2 (II-7) H 2 N-CSNH (CH 2) 2 NHCS-NH 2 (VII-14) HSCH ₂ CH ₂ NHCH ₂ CH ₂ OH In addition to the bleaching accelerators of the present invention exemplified above,
No. 263568, exemplified compounds described on pages 51 to 115, Nos. I-2, I-4 to 7, I-9 to 13, I-16 to 21,
I-23, I-24, I-26, 27, I-30 to 36, I-38, II
-2 to 5, II-7 to 10, II-12 to 20, II-22 to 25, II-
27, II-29 to 33, II-35, 36, II-38 to 41, II-43, II
-45 to 55, II-57 to 60, II-62 to 64, II-67 to 71, II-
73-79, II-81-84, II-86-99, II-101,102, II-1
04-110, II-112-119, II-121-124, II-126, II-
128-144, II-146, II-148-155, II-157, III-
4, III-6-8, III-10,11, III-13, III-15-1
8, III-20, III-22, III-23, III-25, III-27, II
I-29 ~ 32, III-35,36, IV-3, IV-4, V-3 ~
6, V-8-14, V-16-38, V-40-42, V-44-4
6, V-48 to 66, V-68 to 70, V-72 to 74, V-76 to 7
9, V-81,82, V-84-100, V-102-108, V-110,
V-112,113, V116-119, V-121-123, V-125-13
0, V-132 to 144, V-146 to 162, V-164 to 174, V-1
76-184, VI-4, VI-7, VI-10, VI-12, VI-13, V
I-16, VI-19, VI-21, VI-22, VI-25, VI-27-3
4, VI-36, VII-3, VII-6, VII-13, VII-19, VII
Exemplified Compounds (III-2) to (III-3), (III) described in JP-A-63-17455 and pages 22 to 25 of JP-A-63-17455.
-5) to (III-10), (III-12) to (III-45), (I
II-47) to (III-50), (III-52) to (III-54),
Compounds such as (III-56) to (III-63) and (III-65) can be similarly used.

These bleaching accelerators may be used alone or in combination of two or more, and good results are generally obtained in the range of about 0.01 to 100 g per bleach-fix solution. However, in general, when the added amount is too small, the bleaching acceleration effect is small, and when the added amount is excessively large, precipitation may occur to contaminate the silver halide color photographic light-sensitive material to be processed. The amount is preferably 0.05 to 50 g per solution, more preferably 0.05 to 50 g per bleach-fix solution.
15g.

When a bleaching accelerator is added, it may be added and dissolved as it is. However, it is general that the bleaching accelerator is dissolved in water, an alkali, an organic acid, or the like in advance, and then added, and if necessary, methanol, ethanol, acetone, etc. Can be added by dissolving using the above organic solvent.

The bleaching solution of the present invention contains 1.5 mol or less of bromide per bleaching solution.

The bromide used in the bleaching solution of the present invention plays a role of assisting the silver bleaching power by the ferric aminopolycarboxylic acid complex salt, and when used in the bleaching solution, 1.6 mol or more per bleaching solution has conventionally been used.

However, in the present invention, the amount is preferably 1.5 mol or less per bleaching solution. That is, when an aminopolycarboxylic acid ferric complex salt having a weak silver bleaching power is used, a certain bromide concentration is required in order to enhance the silver bleaching power. Since the ferric complex salt is used, bromide does not need to be used as conventionally, and since bromide can be reduced in concentration, it can be concentrated.

Further, by controlling the ferric complex salt and bromide concentration of the present invention to 1.5 mol or less, long-term running, particularly in the case of a small amount of processing, turbing in a bleaching solution (easy to adhere to the tank wall) and silver sludge It was also found that sediment that could be considered was greatly reduced.

The bromide concentration used in the bleaching solution of the present invention is 0.15 mol or more and 1.0 mol or less.

As bromide, ammonium bromide, potassium bromide,
Examples thereof include sodium bromide, and particularly preferred is ammonium bromide, which rapidly diffuses into the film.

The bleaching solution of the present invention includes various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. Becomes pH
The buffer may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents or surfactants can be added.

When the processing solution having a fixing ability according to the present invention is a bleach-fixing solution, the bleaching agent used in the bleach-fixing solution is preferably a ferric complex salt of aminocarboxylic acid or aminophosphonic acid. The aminocarboxylic acid and the aminophosphonic acid represent an amino compound having at least two or more carboxylic acid groups and an amino compound having at least two or more phosphonic acid groups, respectively, and are preferably represented by the following general formula [XI
[I] and [XIII].

General formula [XII] General formula (XIII) Wherein, E is a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene _{group, -R 83 OR 83 OR 83 -} , - R 83
ZR ₈₃ - represents, Z is> N-R ₈₃ -A _6, represents> N-A _6, R
_{79 to} R ₈₃ represent a substituted or unsubstituted alkylene group, and A ₂
To A ₆ represents a hydrogen atom, -OH, -COOM, and -PO ₃ M _2, M represents a hydrogen atom, an alkali metal atom.

Next, preferred specific exemplary compounds of the compounds represented by the general formulas [XII] and [XIII] will be described below.

[Exemplified Compound] [XII-1] Ethylenediaminetetraacetic acid [XII-2] Diethylenetriaminepentaacetic acid [XII-3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetic acid [XII-4] ] 1,3-propylenediaminetetraacetic acid [XII-5] triethylenetetraminehexaacetic acid [XII-6] cyclohexanediaminetetraacetic acid [XII-7] 1,2-diaminopropanetetraacetic acid [XII-8] 1,3- Diaminopropan-2-ol-tetraacetic acid [XII-9] ethyl ether diamine tetraacetic acid [XII-10] glycol ether diamine tetraacetic acid [XII-11] ethylenediamine tetrapropionic acid [XII-12] phenylenediamine tetraacetic acid [XII -13] Disodium ethylenediaminetetraacetate [XII-14] Tetraethylenetriaminetetraacetate Ammonium salt) [XII-15] tetrasodium ethylenediaminetetraacetic acid salt [XII-16] pentasodium diethylenetriaminepentaacetic acid salt [XII-17] ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triamine Sodium acetate [XII-18] Propylene diamine tetraacetic acid sodium salt [XII-19] Ethylene diamine tetramethylene phosphonic acid [XII-20] Cyclohexanediamine tetraacetic acid sodium salt [XII-21] Diethylene triamine pentamethylene phosphonic acid [XII-22] ] Cyclohexanediaminetetramethylenephosphonic acid [XIII-1] nitrilotriacetic acid [XIII-2] methyliminodiacetic acid [XIII-3] hydroxyethyliminodiacetic acid [XIII-4] nitrilotripropionic acid [XIII-5] nitrotrimethylenephosphonic acid [ XIII-6] Iminozi Methylenephosphonic acid [XIII-7] hydroxyethyliminodimethylenephonic acid [XIII-8] Nitrilotriacetic acid trisodium salt Among these aminocarboxylic acids and aminophosphonic acids, compounds which are particularly preferably used from the viewpoint of the effects of the present invention. (XII-1), (XII-2), (XII-
4), (XII-6), (XII-7), (XII-10), (XII
-19), (XIII-1) and (XIII-5). Among them, (XII-4) is particularly preferable in view of the effect of the object of the present invention.

The ferric complex salt of an organic acid according to the present invention may be a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt. Etc., but preferably potassium salts, sodium salts and ammonium salts. At least one kind of these ferric complex salts may be used, but two or more kinds may be used in combination. The amount can be arbitrarily selected, and it is necessary to select the amount according to the amount of silver in the light-sensitive material to be processed, the silver halide composition, and the like. Used at 1.0 mole. In the replenisher, it is desirable to use the replenisher concentrated to the full solubility in order to reduce the concentration.

The preferred replenishing amount of the bleaching solution according to the present invention is 20 ml to 500 ml, preferably 30 ml to 350 ml, more preferably 40 ml to 300 ml, most preferably 50 ml per m ^{2 of the} silver halide color photographic light-sensitive material. Or 250 ml.

A so-called fixing agent is essential for the fixing solution and the bleach-fixing solution according to the present invention.

As a fixing agent, a compound which reacts with silver halide to form a complex salt of an aqueous solution, for example, potassium thiosulfate, sodium thiosulfate, thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; thiourea; thioether;

In addition to these fixing agents, fixing solutions and bleach-fixing solutions also include
One or more pH buffers consisting of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. Can be included.

Further alkali halide or ammonium halide,
For example, it is desirable to contain a large amount of a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. Borate, oxalate, acetate,
PH buffers such as carbonates and phosphates, alkylamines, polyethylene oxides and the like which are known to be added to ordinary fixing solutions and bleach-fixing solutions can be appropriately added.

The fixing agent is used in an amount of 0.1 mol or more per processing solution, and is preferably 0.6 mol or more from the viewpoint of the effects of the present invention.
It is used in the range of 4 mol, particularly preferably in the range of 0.9 mol to 3.0 mol, particularly preferably in the range of 1.1 mol to 2.0 mol.

In the present invention, air or oxygen may optionally be blown in the processing bath and in the processing replenisher storage tank to increase the activity of the bleaching solution or bleach-fixing solution, or a suitable oxidizing agent, for example, Hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

In carrying out the method of the present invention, silver may be recovered from the fixing solution or the bleach-fixing solution by a known method. For example, an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, a German Patent No. 2,331,220), and an ion exchange method (described in Japanese Patent Application Laid-Open No. 51-17114) And the metal substitution method (described in British Patent 1,353,805) can be effectively used.

It is particularly preferable to recover silver in-line from the tank liquid, because the suitability for rapid processing is further improved. However, silver may be recovered from the overflow waste liquid and reused.

When the replenishing amount of the fixing solution and the bleach-fixing solution according to the present invention is 800 ml or less per 1 m ^{2 of the} light-sensitive material, the effects of the present invention can be exhibited more favorably. Especially 20ml ~ ⁶ per m2 of photosensitive material
Significant effects are obtained at 50 ml, especially at 30 ml to 400 ml.

Further, when the fixing solution and the bleach-fixing solution according to the present invention contain 0.1 g / -10 g / iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.) of the present invention. Promote the effect more. Especially 0.3g / ~ 5g /,
Especially especially 0.5 g / ~ 3 g /, most preferably 0.8 g /
Good results are obtained at ~ 2 g /.

When a compound represented by the following general formula [FA] or a compound of the following compound group [FB] is added to a processing solution having a fixing ability (fixing solution or bleach-fixing solution) according to the present invention and used, In the present invention, not only the effect of the object is achieved better, but also the use of a fixing solution or a bleach-fixing solution promotes an effect that extremely little sludge is generated when a small amount of photosensitive material is processed over a long period of time. Is more preferably used.

(In the formula, R ′ and R ″ each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a nitrogen-containing heterocyclic ring. N ′ represents 2 or 3.) Specific examples represented by the general formula [FA] Exemplary compounds are shown below.

These compounds represented by the general formula [FA] are disclosed in US Pat.
It can be synthesized by a general method as described in US Pat. No. 335,161 and US Pat. No. 3,260,718.

Compound group [FB] FB-1 Thiourea FB-2 Ammonium iodide FB-3 Potassium iodide FB-4 Ammonium thiocyanate FB-5 Potassium thiocyanate FB-6 Sodium thiocyanate FB-7 Thiocyanocatechol The compound represented by the formula [FA] and the compound of the compound group [FB] may be used alone or in combination of two or more. For example, thiourea and ammonium thiocyanate and ammonium iodide, thiourea and ammonium thiocyanate, (FA-12) and thiourea, (FA-12) and ammonium thiocyanate, (FA-1
2) and ammonium iodide, (FA-12) and (FA-32), (F
A-12) and (FA-38) are preferred examples.

The amount of the compound represented by the general formula [FA] and the compound of the compound group [FB] is 0.1 g to 20 g per treatment solution.
Good results are obtained in the range of 0 g. Especially, the range of 0.2 g to 100 g is preferable, and the range of 0.5 g to 50 g is particularly preferable.

The pH of the bleaching solution of the present invention is used in the range of 2 to 8, and is preferably in the range of 3 to 7 and particularly preferably in the range of 4 to 6 from the viewpoint of the effect of the present invention. Most preferably, the pH is in the range of 4.5 to 5.8.

The pH of the fixing solution and the bleach-fixing solution of the present invention is used in the range of 4 to 8.

Examples of the sulfite and sulfite releasing compound according to the present invention include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, and the like. No. Furthermore, the following general formula [B-1] or [B-
2] are also included.

General formula [B-1] General formula [B-2] In the formula, R ₁₇ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
₁₈ is an alkyl group having 1 to 5 carbon atoms which may be substituted; M is an alkali metal atom; R ₁₉ and R ₂₀ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted; Represents an integer.

Hereinafter, specific examples of the compound represented by the above general formula will be described, but the present invention is not limited thereto.

Hereinafter, preferred specific examples of the compounds represented by formulas [B-1] and [B-2] are shown.

B-1 Sodium formaldehyde sodium bisulfite B-2 Acetaldehyde sodium bisulfite B-3 Propionaldehyde sodium bisulfite B-4 Butyraldehyde sodium bisulfite B-5 Succinic aldehyde sodium bisulfite B-6 Glutaraldehyde bis sodium bisulfite B- 7 β-Methylglutaraldehyde bisulfite sodium bisulfite B-8 Maleic dialdehyde bisulfite sodium bisulfite These sulfites and sulfurous acid releasing compounds require at least 0.1 mol of sulfuric acid per fixing solution or bleach-fixing solution, but 0.001 mol. The range of mol / の 0.5 mol / is preferred, and the range of 0.05 mol / 〜0.40 mol / is particularly preferred. Particularly preferred is a range of 0.10 mol / -0.30 mol /. However, the number of moles of these sulfites and the sulfite-releasing compound is shown in terms of sulfurous acid.

The processing time of the bleaching solution and the processing solution having a fixing ability (fixing solution or bleach-fixing solution) according to the present invention is preferably 3 minutes and 45 seconds or less in total, and more preferably 20 seconds or less.
The effect of the object of the present invention is excellent when the time is in the range of 3 minutes and 20 seconds, particularly preferably 40 seconds to 3 minutes, particularly preferably 60 seconds to 2 minutes and 40 seconds.

The bleaching time can be arbitrarily selected within the range of the above total time, but is preferably 1 minute and 30 seconds or less, particularly preferably 10 seconds to 70 seconds, particularly preferably 20 seconds to
55 seconds is preferred. The processing time of the processing solution having the fixing ability is as follows.
Although it can be arbitrarily selected within the above total range, it is preferably 3 minutes and 10 seconds or less, particularly preferably 10 seconds to 2 minutes and 40 seconds, particularly preferably 20 minutes, from the viewpoint of the effects of the object of the present invention. The range is from seconds to 2 minutes and 10 seconds.

In the processing method of the present invention, it is preferable to forcibly agitate the bleaching solution, the fixing solution and the bleach-fixing solution. The reason for this is not only that the effects of the object of the present invention can be achieved more favorably, but also from the viewpoint of rapid processing suitability.

Here, forcible liquid stirring means not forced diffusion and movement of liquid but stirring by adding stirring means.

 Forcible stirring means include the following methods.

1.High-pressure spraying or spray stirring 2.Air bubbling 3.Ultrasonic oscillation 4.Vibration High-pressure spraying is a spray nozzle that applies a discharge pressure of 0.1kg / cm ² or more. the treatment liquid refers to method of performing processing by spraying the photosensitive material in the direct treatment liquid, and the spray stirring method, the treatment liquid over the discharge pressure 0.1 kg / cm ² or more pressure from the nozzle directly on treatment solution from A method of spraying a photosensitive material to perform processing, and a pressure pump or a liquid sending pump is generally used as a pressure source. Pressure pumps include plunger pumps, gear pumps, magnet pumps,
There is a cascade pump, for example, Maruyama Seisakusho 15-LP
M type, 10-BFM type, 20-BFM type, 25-BFM type and the like are known as examples.

Further, as a liquid sending pump, for example, MD-8 manufactured by Iwaki Co., Ltd.
Type, MD-10 type, MD-20R type, MD-30R type, MD-55R type, MDK
-25 type and MDK-32 type.

On the other hand, nozzles and spray nozzles have straight-line type, fan type,
There are a circular type, a full type, a ring type, etc., which have a strong impact force and are more effective as the microscopic vibration is applied to the processed photosensitive material. The spray impact force is mainly determined by the flow rate (/ min) and the spray pressure (kg / cm ² ). Therefore, there is a need for a pressurizing device capable of adjusting the pressure in proportion to the number of spray nozzles so as to sufficiently exert the effect. The most preferred pressure is 0.
If it is less than ³ to 10 kg / cm ² , no effect will be obtained, and if it is too large, the photosensitive material may be damaged or damaged.

Next, with the air bubbling treatment method, a sparger is installed at the bottom of the lower transport roller of the processing liquid tank, air or an inert gas is sent to the sparger, and the photosensitive material is vibrated by bubbles discharged from the mouth. And a method in which a processing solution is effectively brought into contact with the front, back and side surfaces of the photosensitive material. Suitable materials for the sparger are corrosion-resistant materials such as hard PVC, stainless steel coated with polyethylene, sintered metal, etc., and the diameter of the perforation is such that the discharged air bubbles are from 2 mm to 30 mm. From 5mm to 15mm
A better result can be obtained. Examples of the method of sending air include an air compressor, for example, a Bebicon (0.4KW, BU7TL) manufactured by Hitachi, Ltd., and an air pump, for example, an air pump (Ap220 type) manufactured by Iwaki. The amount of air is 2 per transported rack of the automatic processor.
30 / min to 30 / min required, 5 / min to 20 / m
With in, a more favorable result is obtained. The amount of air or inert gas must be adjusted according to the size of the processing solution tank and the amount of photosensitive material, but the air or inert gas must be adjusted so that the vibration width of the photosensitive material due to air bubbles is from 0.2 mm to 20 mm. It is preferred to send the quantity.

Next, the ultrasonic oscillation processing method is a method in which an ultrasonic oscillator is installed in the space of the bottom or side wall in the processing solution tank of the automatic developing machine, and the photosensitive material is irradiated with ultrasonic waves to enhance the development promoting effect. . As the ultrasonic oscillator, for example, a magnetostrictive nickel vibrator (horn type) or a magnetostrictive barium titanate vibrator (holder type) manufactured by Ultrasonic Industrial Co., Ltd. is used.

The oscillator frequency of the ultrasonic oscillator is 5-1000KHz
Of these, those having a frequency of 10 to 50 KHz are particularly preferred in view of the effects of the present invention and damage to the equipment of the automatic developing machine. As the method of irradiating the photosensitive material with the ultrasonic wave, the photosensitive material may be irradiated directly or indirectly by providing a reflection plate. However, since the ultrasonic wave is attenuated in proportion to the irradiation distance, the direct irradiation may be performed. It is more preferable to do so. The irradiation time is preferably at least one second. When the irradiation is partially performed, any of an initial stage, a middle stage, and a late stage of the treatment process may be used.

Further, the vibration processing method is a method in which a photosensitive material is vibrated effectively between the upper roller and the lower roller in a processing solution tank of an automatic developing machine to effectively perform immersion processing.
As the vibrator of the vibration source, for example, V-2B and V-4B types manufactured by Shinko Electric Co., Ltd. are generally used. The vibrator is installed in such a manner that the vibrator is fixed on the upper part of the immersion processing tank of the automatic developing machine, and the vibrator is applied from the back side of the photosensitive material. Vibrator frequency is 100 to 10,000 times / min
Is preferred. The most preferred range is 500-6000 cycles / min. The amplitude of the light-sensitive material to be processed is 0.2 mm to 30 mm, preferably 1 mm to 20 mm. If it is lower than this, there is no effect, and if it is too large, the photosensitive material may be damaged. The number of oscillators varies depending on the size of the automatic developing machine. However, when the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing one or more at least one processing tank in each processing tank.

In the present invention, after processing with the bleaching solution of the present invention, processing is immediately performed with a processing solution having a fixing ability (fixing solution or bleach-fixing solution). That is, when a ferric complex salt having a high aeration rate, as found in a ferric complex salt of ethylenediaminetetraacetic acid, enters a fixing solution or a bleach-fixing solution, it reacts with sulfite ions to stabilize the solution of the fixing solution or the bleach-fixing solution itself. The properties were easily impaired, and the liquid stability in the post-bath was adversely affected.

Although the ferric complex salt of the present invention used in the bleaching solution has strong oxidizing power, the ferrous complex salt as a reductant is very stable, so that it is stable in a fixing solution or a bleach-fixing solution.
For example, silver sulfide formation does not occur even in a washing or a washing substitute liquid or a washing substitute stable liquid, and stable performance can be obtained.

 Further, there is a merit that speeding up can be achieved.

Preferred specific processing steps of the processing method according to the present invention are shown below.

(1) Color development → bleaching → fixing → washing (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Color developing → bleaching → fixing → first stable → first 2 Stable (5) Color development → Bleaching → Bleaching and fixing → Washing (6) Color developing → Bleaching → Bleaching and fixing → Washing → Stable (7) Color developing → Bleaching → Bleaching and fixing → Stable (8) Color developing → Bleaching → Bleaching and fixing → 1st stability → 2nd stability Among these processes, (3), (4),
(7) and (8) are preferable, and particularly (3),
(4) is preferred.

The color developer according to the present invention may contain an alkali agent usually used in the developer, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And further contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfite. You may.

Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the developer according to the present invention is usually 7 or more, preferably about 9 to 13.

In the color developer used in the present invention, hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, bentose or Hexose, pyrogallol-1,3
-Dimethyl ether or the like may be contained.

In the color developing solution according to the present invention, various chelating agents can be used in combination as a sequestering agent. Examples of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminopolycarboxylic acids such as aminotri (methylenephosphonic acid) and ethylenediaminetetraphosphoric acid. Examples include oxycarboxylic acids such as phosphonic acid, citric acid and gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.

In the present invention, the effect of the object of the present invention, in particular, the preservability of the dye image is improved when processing is carried out with a stabilizing solution subsequent to a fixing solution or a bleach-fixing solution.

The replenishment amount of the stabilizing solution according to the present invention is 1 to 80 times, particularly preferably 2 to 60 times, the carry-in amount from the previous bath per unit area of the color photographic light-sensitive material for photography to be processed. In the present invention, the concentration of the pre-bath component (bleach-fixing solution or fixing solution) in the stabilizer is 1/500 in the last tank of the stabilizer.
The following is more preferable, and particularly preferable is 1/1000 or less. Furthermore, 1/500 to 1/100 in terms of low pollution and liquid storage
000 is preferable, and more preferably 1/2000 to 1/50000, the treatment tank of the stabilization tank is constituted.

The stabilization tank is preferably composed of a plurality of tanks, and the plurality of tanks is preferably two tanks or more and six tanks or less.

The effect of the present invention is that the stabilization treatment tank is 2 tanks or more and 6 tanks or less, and that a counter current method (a method of supplying to a post-bath and overflowing from a pre-bath) is used.
It is particularly preferable from the viewpoint of low pollution and improvement of image preservation. Particularly preferably, two or three tanks are used, and more preferably two tanks.

The carry-in amount varies depending on the type of photosensitive material, the transport speed of the automatic developing machine, the transport method, the squeezing method of the photosensitive material surface, etc. 50ml / m
² is ~ 150 mL / m ^2, replenishment rate effect is more pronounced in the present invention for this amount carried is in the range of ^{50ml / m 2 ~4.0 / m 2} , the effect is particularly noticeable replenishment rate 200 ml / m ² ~ 1500ml
/ m ² range.

The treatment temperature of the treatment with the stabilizing solution is 15 to 60 ° C, preferably
The range of 20 to 45 ° C is good.

Further, in the stabilizer according to the present invention, the following general formula [VI
It is preferable to include the chelating agents represented by I '] to [IX'] in order to improve the white background of the unexposed areas and prevent yellow stain of the dye image after storage.

General formula [VII '] (Wherein, E is an alkylene group, a cycloalkylene group, a phenylene _{group, -R 5 -O-R 5 -} , - R 5 -O-R 5 -O-R 5 - or -R ₅ -Z-R ₅ - Z represents> NR ₅ -A ₅ , Represents R _{1 to} R ₃ each represent an alkylene group. A _{1 to} A ₃
Each represents a -COOM or -PO ₃ M _2, A ₄ and A ₅ are each a hydrogen atom, a hydroxyl group, a -COOM or -PO ₃ M _2. M represents a hydrogen atom or an alkali metal atom. ) General formula [VIII '] (In the formula, R ₇ represents an alkyl group, an aryl group or a nitrogen-containing 6-membered ring group; M represents a hydrogen atom or an alkali metal atom.) [IX ′] (Wherein R ₈ , R ₉ and R ₁₀ are each a hydrogen atom, a hydroxyl group,-
COOM, --PO ₃ M ₂ or an alkyl group, B ₁ , B ₂ and B ₃ are each a hydrogen atom, a hydroxyl group, --COOM, --PO ₃ M ₂ or Represents J represents a hydrogen atom, an alkyl group, -C ₂ H ₄ OH or -
Represents PO ₃ M ₂ . M represents a hydrogen atom or an alkali metal atom, and n and m each represent 0 or 1.

Some specific examples of the chelating agents represented by the general formulas [VII '], [VIII'], and [IX '] are shown below. The chelating agent used in the present invention is not limited to the following specific examples.

[Example chelating agent] The chelating agent preferably used in the stabilizer is preferably used in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.1 to 20 g, per 1 stabilizer.
It is.

The pH of the stabilizer preferably used in the present invention is preferably in the range of pH 4.0 to 9.0, more preferably pH 4.10, for the purpose of improving image storability, in addition to the effects of the present invention.
It is in the range of 5-9.0, particularly preferably in the range of 5.0-8.5.

As the pH adjuster that can be contained in the stabilizing solution preferably used in the present invention, any commonly known alkali agent or acid agent can be used.

Stabilizing liquids preferably used in the present invention include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.), Surfactants, preservatives, Bi, Mg, Zn, Ni, Al, Sn,
Metal salts such as Ti and Zr can be added. These compounds may be used in any combination in an amount that is necessary to maintain the pH of the stabilizing bath according to the present invention and that does not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. I don't mind.

Anti-binders preferably used in the stabilizer of the present invention are hydroxybenzoic acid ester compounds, phenolic compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, Ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen releasing compounds, and benztriazole compounds.

The hydroxybenzoic acid ester compound includes hydroxybenzoic acid methyl ester, ethyl ester, propyl ester, butyl ester and the like, preferably hydroxybenzoic acid n-butyl ester, isobutyl ester, propyl ester, more preferably It is a mixture of the three hydroxybenzoic esters.

The phenolic compound preferably used as the anti-binder agent of the present invention includes an alkyl group, a halogen atom, a nitro group,
It is a compound which may have a hydroxyl group, a carboxylic acid group, an amino group, a phenyl group or the like as a substituent, and is preferably orthophenylphenol and orthocyclohexylphenol, phenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol It is. Particularly preferably, orthophenylphenol exhibits remarkable anti-bism property in combination with the bisulfite adduct of an aldehyde derivative.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazoline-3-one, 2-octyl-4-isothiazoline. 3-one, 5-chloro-2-methyl-4-isothiazoline 3-
On, 2-chloro-4-thiazolyl-benzimidazole.

Specific examples of the pyridine-based compound include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, sodium-2-pyridinethiol-1-oxide and the like, and preferably sodium-2-pyridinethiol-1. -An oxide.

Specific examples of the guanidine-based compound include cyclohexidine, polyhexamethylenebiguanidine hydrochloride, dodecylguanidine hydrochloride and the like, and preferably dodecylguanidine and its salts.

The carbamate compound is specifically methyl-1-
(Butylcarbamoyl) -2-benzimidazole carbamate, methylimidazole carbamate and the like.

Specific examples of the morpholine-based compound include 4- (2-nitrobutyl) morpholine and 4- (3-nitrobutyl) morpholine.

The quaternary phosphonium-based compound includes a tetraalkylphosphonium salt and a tetraalkoxyphosphonium salt, and is preferably a tetraalkylphosphonium salt, and a more specific preferred compound is tri-n-butyl-.
Tetradecylphosphonium chloride and tri-phenylnitrophenylphosphonium chloride.

Specific examples of the quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridium salts.Specifically, dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, laurylpyridinium chloride Etc.

The urea-based compound is specifically N- (3,4-dichlorophenyl) -N '-(4-chlorophenyl) urea, N-
(3-trifluoromethyl) -N '-(4-chlorophenyl) urea and the like.

Specific examples of the isoxazole-based compound include 3-hydroxy-5-methyl-isoxazole.

The propanol amino compounds include n-propanols and isopropanols. Specifically, DL-2-benzylamino-1-propanol and 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
1-propanol, 3-amino-1-propanol, idpropanolamine, diisopropanolamine, N,
N-dimethyl-isopropanolamine and the like.

Examples of the sulfamide compounds include o-nitrobenzenesulfamide, p-aminobenzenesulfamide,
Chloro-3,5-dinitrobenzenesulfamide, α-amino-p-toluenesulfamide and the like.

The amino acid-based compound specifically includes N-lauryl-β-alanine.

Examples of the active halogen releasing compound include sodium hypochlorite, chloramine T dichloroisocyanurate, chloramine B, dichlorodimethylhydantoin and chlorobromodimethylhydantoin, and sodium hypochlorite, sodium dichloroisocyanurate, and trichloroisocyanurate. Acids are preferred.

Specific examples of the benztriazole-based compound include the following.

(A) Benztriazole Compounds preferably used in the present invention among the above anti-binders are phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, active halogen releasing compounds, and benztriazole compounds. Further, particularly preferred are phenol compounds, thiazole compounds, active halogen releasing compounds and benzotriazole compounds in view of the liquid storage stability.

If the amount of the anti-bubble agent added to the stabilizing solution is 0.001 g or less per liter of the stabilizing solution, the effect of the present invention is not achieved, and
If the amount exceeds g, it is not preferable in terms of cost, and the storage stability of the dye image is further deteriorated. Therefore, the amount is used in the range of 0.001 to 50 g, preferably 0.005 to 10 g.

In the processing of the present invention, silver may be recovered by various methods from a processing solution containing a soluble silver salt such as a fixing solution and a bleach-fixing solution, as well as a stabilizing solution. For example, an electrolysis method (described in the specification of French Patent No. 2,299,667), a precipitation method (JP-A-52-73037)
Patent Publication, West German Patent 2,331,220), ion exchange method (JP-A-51-17114, German Patent 2,54)
No. 8,237) and metal replacement method (UK Patent 1,35
3,805) can be used effectively.

Further, upon silver recovery, the soluble silver salt is recovered as an overflow solution of the processing solution, silver is recovered by the above method, and the remaining solution may be disposed of as a waste solution, or a regenerant may be added, and a replenisher or a tank processing solution may be used. May be used. It is particularly preferred to recover the silver after mixing the stabilizer with the fixer or the bleach-fixer.

Further, a treatment of bringing the stabilizer of the present invention into contact with an ion exchange resin, an electrodialysis treatment (see Japanese Patent Application No. 59-96352), a reverse osmosis treatment (see Japanese Patent Application No. 59-96532), and the like can also be used.

Further, it is preferable to use water obtained by previously deionizing water used for the stabilizing solution of the present invention since the anti-blur property of the stabilizing solution, the stability of the stabilizing solution, and the image storability are improved. As a means of the deionization treatment, any means may be used as long as the dielectric constant of the washed water after the treatment is 50 μs / cm or less, or Ca and Mg ions are 5 ppm or less, for example, an ion exchange resin or a reverse osmosis membrane. It is preferable to use the treatment alone or in combination. The ion exchange resin and the reverse osmosis membrane are described in detail in JP-A-87-1984, but it is preferable to use a strongly acidic H-type cation exchange resin and a strongly basic OH-type anion exchange resin.

In the present invention, when the salt concentration in the stabilizing solution is 1,000 ppm or less, preferably 800 ppm or less, the washing effect is enhanced, and the white background is improved and the anti-blur property is excellent.

The processing time of the stabilizer in the present invention is 2 minutes or less, preferably 1 minute and 30 seconds or less, particularly preferably 1 minute or less in order to exhibit the effects of the present invention, particularly the effect on the processing stabilizer.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the average silver iodide content of all silver halide emulsions in the silver halide photographic light-sensitive material is preferably from 0.1 to 15 mol%, more preferably. Is from 0.5 to 12 mol%, particularly preferably from 1 to 6 mol%.

In the method for processing a silver halide color photographic material of the present invention, the average grain size of all silver halide emulsions in the silver halide color photographic material is preferably 2.0 μm or less, more preferably 0.1 to 1.0 μm or less, and particularly preferably. Is from 0.2
0.6 μm.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the lower limit of the total of the dry film thicknesses of all the hydrophilic colloid layers of the silver halide color photographic light-sensitive material (hereinafter referred to as the film thickness of the emulsion surface) is included. Silver halide emulsion, coupler,
The thickness of the emulsion surface is preferably 5 to 18 μm, more preferably 10 to 16 μm, although there is a limit depending on the oil and additives.

The thickness is preferably 14 μm or less from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support, and 10 μm from the emulsion layer which is different in color sensitivity from the emulsion layer to the lower end of the emulsion layer next to the support.
μm or less is preferred.

The light-sensitive material according to the present invention is prepared by an internal developing method in which a coupler is contained in the light-sensitive material (US Pat. No. 2,376,679;
No. 2,801,171), and any coupler generally known in the art can be used. For example, cyan couplers include those having a naphthol or phenol structure as a base and forming an indoaniline dye by coupling, and magenta couplers having a 5-pyrazolone ring having an active methylene group as a skeleton structure and pyrazoloazole-based compounds. ,
Further, for example, as the yellow coupler, any of those having a benzoylacetanilide, pivalyl acetanilide, acylacetoanilide structure having an active methylene ring and having a substituent at a coupling position, and those having no substituent can be used. Thus, as a coupler, a so-called 2
Equivalent couplers and 4-equivalent couplers can be used.

Hereinafter, the coupler preferably used in the present invention will be described in detail.

As the cyan coupler, the following general formulas [CA] and [C
-B] and [CC].

General formula [CA] General formula [CB] (Wherein, R ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and Y is A group represented by -CONHCOR ₂ or -CONHSO ₂ R ₂ (where R ₂ is an alkyl group, an alkenyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group, and R ₃ represents a hydrogen atom or a group represented by R ₂ . R ₂ and R ₃ may be the same or different, and may combine with each other to form a 5- to 6-membered heterocycle. ) And Z represent a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. ) General formula [CC] R ₁ is -CONR ₄ R ₅ , -NHCOR ₄ , -NHCOOR ₆ , -NHSO ₂ R ₆ ,
-NHCONR ₄ R ₅ or -NHSO ₂ NR ₄ R ₅ , R ₂ is a monovalent group, R ₃ is a substituent, X is a hydrogen atom or a group which is released by reaction with an oxidized aromatic primary amine developing agent, l is 0 or 1, m is 0
3, R ₄ and R _{5 each} represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, R ₆ represents an aromatic group, an aliphatic group or a heterocyclic group, and when m is 2 or 3, each R ₃ may be the same or different, may combine with each other to form a ring, and R ₄ and R ₅ , R ₂
And R ₃ , and R ₂ and X may combine to form a ring. Where l
Is 0, m is 0, R ₁ is —CONHR ₇ , and R ₇ represents an aromatic group.

First, the general formulas [CA] and [CB] will be described. In the formula, Y is It is a group represented by -CONHCOR ₂ or -CONHSO ₂ R ₂ . Here, R ₁ and R ₂ are each an alkyl group, preferably 1 to 1 carbon atoms.
20 alkyl groups (e.g. methyl, ethyl, t-butyl,
Dodecyl, etc.), alkenyl group, preferably 2 carbon atoms
~ 20 alkenyl groups (such as allyl group and heptadecenyl group), cycloalkyl groups, preferably those having a 5- to 7-membered ring (such as cyclohexyl), aryl groups (such as phenyl group, tolyl group, naphthyl group and the like), and heterocyclic rings Group, preferably a nitrogen, oxygen or sulfur atom from 1 to 4
5-membered to 6-membered ring groups (e.g., furyl group, thienyl group,
Benzothiazolyl group). R ₃ is a hydrogen atom or
A group represented by R _2. R ₂ and R ₃ are combined with each other to form 5-6
May form a membered heterocycle. Any substituents can be introduced into R ₁ and R ₂ , for example, having 1 to 10 carbon atoms.
(E.g., methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.), an aryl group (e.g., phenyl, naphthyl, etc.), a halogen atom (fluorine, chlorine, bromine, etc.), cyano, nitro, Sulfonamide groups (eg, methanesulfonamide, butanesulfonamide, p
-Toluenesulfonamide, etc.), sulfamoyl group (methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl group, carbamoyl group (eg, dimethylcarbamoyl, phenylcarbamoyl, etc.) ), An oxycarbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl, etc.), an acyl group (eg, acetyl, benzoyl, etc.), a heterocycle (eg, a pyridyl group,
Pyrazolyl group), an alkoxy group, an aryloxy group,
An acyloxy group and the like can be mentioned.

In the general formulas [CA] and [CB], R ₁
Represents a cyan coupler represented by the general formulas [CA] and [CB] and a ballast group necessary for imparting diffusion resistance to the cyan dye formed from the cyan coupler. It is preferably an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group. For example, a linear or branched alkyl group (for example, t-
Butyl, n-octyl, t-octyl, n-dodecyl, etc.) and a 5- or 6-membered heterocyclic group.

In the general formulas [CA] and [CB], Z
Represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of an N-hydroxyalkyl-substituted-p-phenylenediamine derivative color developing agent. For example, a halogen atom (eg, chlorine, bromine, fluorine, etc.), a substituted or unsubstituted alkoxy group, an aryloxy group, a heterocyclic oxy group,
Acyloxy group, carbamoyloxy group, sulfonyloxy group, alkylthio group, arylthio group, heterocyclic thio group, sulfonamide group and the like.More specific examples are U.S. Pat.No. 3,741,563, JP-A-47-37425, JP-B-48-36894, JP-A-50-10135, 50-117422
No. 50-130441, No. 51-108841, No. 50120343,
Nos. 52-18315, 53-105226, 54-14736, 54
-48237, 55-32071, 55-65957, 56-193
No. 8, No. 56-12643, No. 56-27147, No. 59-146050
Nos. 59-166696, 60-24547, 60-35731,
Nos. 60-37557 and the like. In the present invention, a cyan coupler represented by the general formula [CD] is preferable.

General formula [CD] In the general formula [CD], R ₄ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent includes -SO
₂ R ₅ , halogen atom (fluorine, chlorine bromine, etc.), -CF ₃ ,-
_{NO 2, -CN, -COR 5,} -COOR 5, -SO 2 OR 5, −OR ₅ , −OCOR ₅ , And at least one substituent selected from the group consisting of:

Here, R ₅ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, ethyl, t-butyl, dodecyl and the like), an alkenyl group, preferably 2 to 20 carbon atoms.
Alkenyl group (such as allyl group and heptadecenyl group), cycloalkyl group, preferably those having a 5- to 7-membered ring (such as cyclohexyl), and aryl group (such as phenyl group,
R ₆ is a hydrogen atom or a group represented by R ₅ .

Preferred compounds of the cyan coupler of the present invention represented by the general formula [CD] are those in which R ₄ is a substituted or unsubstituted phenyl group, and the substituent on the phenyl group is cyano, nitro,
—SO ₂ R ₇ (R ₇ is an alkyl group) is a compound such as a halogen atom and trifluoromethyl.

In the general formula [CD], Z and R ₁ each represent the general formula [C
-A] and [CB]. Preferred examples of the ballast group represented by R ₁ are those represented by the following general formula [C-
E].

General formula [CE] In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, 1 represents 0 or 1, and K represents
There is R ₉ where there are two or more in the case of more than one may be the same or different, R ₈ represents a substituted alkylene group such as a straight-chain or branched, and aryl groups having 1 to 20 carbon atoms, R ₉ is Represents a monovalent group, preferably a hydrogen atom, a halogen atom (for example, chromium or bromo), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, t-butyl, t-pentyl) , T-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl group (for example, phenyl group), heterocyclic group (for example, nitrogen-containing heterocyclic group), alkoxy group, preferably linear or branched carbon number 1 to 20 alkoxy groups (for example, methoxy, ethoxy,
t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy group (eg, phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (eg, acetooxy group, benzoyloxy) Group), carboxy, alkyloxycarbonyl group, preferably linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably phenoxycarbonyl group, alkylthio group, preferably acyl group having 1 to 20 carbon atoms, preferably carbon atom A linear or branched alkylcarbonyl group of numbers 1 to 20,
An acylamino group, preferably a linear or branched alkylcarbonamide group having 1 to 20 carbon atoms, a benzenecarbamide group, a sulfonamide group, preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms or benzenesulfone Amido group, carbamoyl group, preferably having 1 to 1 carbon atoms
20 represents a linear or branched alkylaminocarbonyl group or a phenylaminocarbonyl group, a sulfamoyl group, preferably a linear or branched alkylaminosulfonyl group or a phenylaminosulfonyl group having 1 to 20 carbon atoms.

Next, specific examples of the cyan coupler of the present invention represented by the general formula [CA] or [CB] are shown below, but the invention is not limited thereto.

(Exemplary compound)

Next, the general formula [CC] will be described.

Each group represented by R _{2 to} R ₇ in the general formula [CC] includes those having a substituent.

As R ₆ is an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms Preferably, R _4,
As R ₅ , a hydrogen atom and those described as preferable as R ₆ are preferable.

As R ₂ , a hydrogen atom bonded to NH directly or via NH, CO or SO ₂ , an aliphatic group having 1 to 30 carbon atoms, and 6 carbon atoms
To 30 aromatic groups, a heterocyclic group having 1 to 30 carbon atoms, -OR ₈ ,
−COR _{8 -POOR 10) 2, -POR 10)} 2, -CO 2 R 10, -SO 2 R 10
Or -SO ₂ OR ₁₀ (R ₈ , R ₉ and R ₁₀ are each R ₄ ,
Same as defined for R ₅ and R ₆ , R ₈ and R ₉
May combine to form a heterocyclic ring. Is preferred.

R ₇ is preferably an aromatic group having 6 to 30 carbon atoms, R ₇
Representative examples of the substituents include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and a ureido Group, acyl group, acyloxy group, aliphatic oxy group,
Aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, aliphatic group, aliphatic oxycarbonyl group, etc. Can be. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, and examples thereof include a dioxymethylene group.

Representative examples of R ₃ include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and a ureido group. An acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, an imide group, etc. Can be mentioned. this
The number of carbon atoms contained in R ₃ is preferably 0 to 30. When m = 2, examples of the cyclic R ₃ include a dioxymethylene group.

When 1 is 1, R ₁ is particularly preferably —CONR ₄ R ₅ , m is preferably 0, and R ₂ is —COR ₈ , —COO directly bonded to NH.
R ₁₀ , —SO ₂ R ₁₀ , —CONR ₈ R ₉ , and —SO ₂ NR ₈ R ₉ are particularly preferred, and more preferred are —COOR ₁₀ , — directly bonded to NH.
COR ₈ and —SO ₂ R ₁₀ , among which —COOR ₁₀ is most preferred.

Further, those forming a dimer or more multimer via R _{1 to} R ₃ and X are also included in the present invention.

Among the general formulas [CC], it is preferable that l = 0.

Specific examples of the coupler represented by the general formula [CC] are described in JP-A-60-237448, JP-A-61-153640, JP-A-61-145557 and JP-A-61-145557.
No. 62-85242, No. 48-15529, No. 50-117422, No. 52-
No. 18315, No. 52-90932, No. 53-52423, No. 54-48237
No. 54-66129, No. 55-32071, No. 55-65957,
No. 55-105226, No. 56-1938, No. 56-12643, No. 56
-27147, 56-126632, 58-95346 and U.S. Pat. No. 3,488,193, and can be synthesized by the methods described therein.

Depending on the physical properties (eg, solubility) of the coupler, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent, an alkali dispersion method of adding as an alkaline solution, and a latex dispersion may be used depending on the physical properties (eg, solubility) of the coupler. Various methods can be used, such as a solid dispersion method in which a solid is directly added as a fine solid.

The amount of the coupler to be added is usually 1.0 per mole of silver halide.
× 10 ⁻³ mol to 1.0 mol, preferably 5.0 × 10 ⁻³ mol to 8.0
× 10 ^-1 mol.

Next, typical specific examples of the coupler represented by the general formula [CC] are shown, but the present invention is not limited thereto.

[Exemplary compound] The silver halide emulsion that can be used in the present invention is preferably a tabular silver halide emulsion, and in addition, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, Any silver halide such as silver iodobromide and silver chloroiodobromide may be used. As the protective colloid of silver halide, various kinds of synthetic colloids can be used in addition to natural substances such as gelatin. The silver halide emulsion may contain usual photographic additives such as a stabilizer, a sensitizer, a hardener, a sensitizing dye, and a surfactant.

As the photosensitive material used in the present invention, any of color negative film, color paper, color reversal film, color reversal paper and the like can be used.

[Effects of the Invention] According to the present invention, precipitation of bleaching components at low temperatures, generation of tar during running, generation of precipitates is small, and rapid processing is possible, and stable regardless of the processing amount. Photographic performance can be obtained.

[Examples] Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Reference Example 1 The following bleaching solution was prepared.

[Bleaching tank liquid] Ammonium ferric aminopolycarboxylate listed in Table 1 Aminopolycarboxylate disodium (free chelating agent for ferric complex salt) 0.01 mol Ammonium bromide Described in Table 1 Glacial acetic acid 10 ml Add water Adjust to 1 and adjust to pH 5.5 using ammonium water or glacial acetic acid.

After adjustment, put 100ml into a screw tube and freeze at -20 ° C.
After the thawing (1 cycle) was repeated for 4 cycles, the precipitateability after thawing was observed.

 However, the following evaluation was performed for the precipitation property.

：: No precipitation, Δ: Slight precipitation, ×: Large precipitation In the table, (A-1) Fe, (A-2) Fe and (A-4) F
e means ferric ammonium salts of (A-1), (A-2) and (A-4), respectively.

As can be seen from Table 1, it can be seen that as the concentration of the aminopolycarboxylic acid ferric complex salt and the concentration of ammonium bromide are increased, precipitation is easy in a low-temperature to normal-temperature cycle (precipitation).

Reference Example 2 In all Examples, the amount of addition in the silver halide photographic light-sensitive material indicates g per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver.

On a triacetylcellulose film support, each layer having the following composition was sequentially formed from the support side to prepare Sample 1 of a multilayer color photographic light-sensitive material.

Sample 1 (comparative) First layer: Antihalation layer (HC-1) Black colloidal silver 0.22 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored coupler (CM-1) 0.05 High boiling point solvent (oil-1) ... 0.20 Gelatin ... 1.4 Second layer: Intermediate layer (IL-1) Ultraviolet absorber (UV-1) ... 0.01 High boiling point solvent (oil-1) ... 0.01 Gelatin ... 1.4 Third layer : Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 1.0 Silver iodobromide emulsion (Em-2) 0.75 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) ... 1.0 × 10 ^-4 (mol / silver 1 mol) 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: 1.4 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) ... 0.15 × 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) ... 0.075 High boiling point solvent (oil-1) ... 0.5 Gelatin ... 1.4 5th layer: Intermediate layer (IL-2) Gelatin ... 0.3 6th layer: Low sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) ... 1.2 Sensitizing dye (S-4) 5.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 1.5 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M'-1) 0.5 Colored magenta coupler (CM- 1) ... 0.05 DIR compound (D-3) ... 0.015 DIR compound (D-4) ... 0.020 High boiling solvent (oil-2) ... 0.5 Gelatin ... 1.0 7th layer: Intermediate layer (IL-3) Gelatin ... 0.7 High boiling solvent (Oil-1) ... 0.15 8th layer: high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) ... 1.5 sensitizing dye (S-6) ... 1.5 x ^10-4 (mol / silver) 1 mol) Sensitizing dye (S-7): 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8): 0.75 × 10 ⁴ (mol / silver 1 mol) Magenta coupler (M′-) 2) ... 0.06 Magenta coupler (M'-3) ... 0.18 Colored magenta coupler (CM-2) ... 0.05 DIR compound (D-3) ... 0.01 High boiling solvent (oil-3) ... 0.5 Gelatin ... 1.0 Ninth layer: Yellow filter layer (YC) Yellow colloidal silver ... 0.1 Color stain inhibitor (SC-1) ... 0.1 High boiling point solvent (oil-3) ... 0.1 Gelatin ... 0.8 10th layer: Low sensitivity blue-sensitive milk Layer (BL) Silver iodobromide emulsion (Em-1) ... 0.25 Silver iodobromide emulsion (Em-2) ... 0.30 Sensitizing dye (S-10) ... 7.0 × 10 -4 ( mol / mole of silver) Yellow Coupler (Y'-1) 0.6 Yellow coupler (Y'-2) 0.12 DIR compound (D-2) 0.01 High boiling solvent (oil-3) 0.15 Gelatin 1.0 Layer 11: High-sensitivity blue-sensitive emulsion Layer (BH) Silver iodobromide emulsion (Em-4) ... 0.50 Silver iodobromide emulsion (Em-1) ... 0.20 Sensitizing dye (S-9) ... 1.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-10) 3.0 × 10 ^4- (mol / silver 1 mol) Yellow coupler (Y'-1) 0.36 Yellow coupler (Y'-2) 0.06 High boiling point solvent (oil-3) 0.07 Gelatin: 1.1 12th layer: 1st protective layer (Pro-1) Fine grain silver iodobromide emulsion: 0.4 (average particle size: 0.08 µm, AgI: 2 mol%) UV absorber (UV-1): 0.10 UV absorber ( UV-2) 0.05 high boiling 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 13th layer: 2nd protective layer (Pro- 2) Surfactant (Su-1) ... 0.005 Alkali-soluble matting agent (average particle size 2 µm) ... 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 composition, each layer has a coating aid Su-2, a dispersion aid Su-3, hardeners H-1 and H-2, and a preservative DI-.
1. Stabilizer Stab-1 and antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.48 μm, average silver iodide content 7.5% Monodisperse surface low silver iodide-containing emulsion Em-2 Average grain size 0.34 μm, average silver iodide content 2.2% Monodisperse Emulsion with uniform composition Em-3 Average grain size 0.80 μm, average silver iodide content 6.2% Monodisperse surface-low silver iodide-containing emulsion Em-4 Average grain size 0.95 μm, average silver iodide content 7.8% Monodisperse surface-low silver iodide-containing emulsions Em-1, Em-3 and Em-4 are described in JP-A-60-138538,
It is a silver iodobromide emulsion having a multilayer structure adjusted with reference to each publication of JP-A No. 61-245151 and mainly comprising an octahedron.

In each of Em-1 to Em-4, the average value of the particle diameter / particle thickness is 0.97, and the width of the particle distribution is 1 respectively.
4, 10, 12 and 11%.

The thus-prepared sample was exposed to wedges using white light, and then subjected to the following development processing.

<Experimental processing> Processing step Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38 ° C Bleaching (1 tank) 45 seconds 38 ° C Fixed (1 tank) 1 minute 30 seconds 38 ° C Stabilization (3 tanks) Cascade) 1 minute 38 ° C. Drying (40 ° C. to 80 ° C.) 45 seconds The composition of the processing solution used is as follows.

[Color developing tank solution] 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-hydroxylethyl) aniline sulfate 4.8 g Potassium hydroxide 1.2 g Add water to make 1 and adjust to pH 10.06 with potassium hydroxide or 50% sulfuric acid.

[Bleaching tank solution] Bleaching solution No. 1 to 25 used in Example 1 [Fixing tank solution] Ammonium thiosulfate 200 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetate 0.5 g Sodium carbonate 10 g Add water And adjust the pH using acetic acid and aqueous ammonia.
Adjust to 7.0.

[Stabilized tank liquid] formaldehyde (37% solution) 2 ml 5-chloro-2-methyl-4-isothiazoline-3-
ON 0.05g Emulgen 810 1ml Formaldehyde sodium bisulfite adduct 2g Water was added to 1 and adjusted to pH 7.0 with ammonium water and 50% sulfuric acid.

After performing the processing in Reference Example 1, the amount of residual silver in the highest density part was measured by a fluorescent X-ray method. However, the time from the color developing solution to the bleaching solution was 5 seconds.

 Table 2 shows the results.

As is clear from Table 2, when the concentration of the ferric complex of ethylenediaminetetraacetic acid and the concentration of ammonium bromide are increased, the bleaching power is increased to some extent, but the desilvering property is considerably poor. When the concentration of ammonium bromide is increased to a certain level or more, the desilvering property tends to be rather deteriorated. On the other hand, when the bleaching agents of the present invention, A-1, A-2 and A-4, are used, they have excellent bleaching power and good desilverability. However, even when the bleaching agent of the present invention was used, it was found that the bleaching power was poor when the bromide concentration was high.

Reference Example 3 A running process was performed using the color negative film and the processing solution prepared in Reference Example 2, and using the following replenisher.

 The composition of the processing solution used is as follows.

[Color developing 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-hydroxylethyl) aniline sulfate 6.0 g Potassium hydroxide 2 g Add water to make 1 and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

The composition of the bleach replenisher used was the same as that of the bleach tank except that the bleach concentration of the bleach tank was 1.5 times.

[Fixing replenisher] Ammonium thiosulfate 200 g Anhydrous sodium bisulfite 15 g Sodium metabisulfite 3 g Disodium ethylenediaminetetraacetate 0.8 g Sodium carbonate 14 g Add water to 1 to adjust to pH 6.5.

The stabilizing replenisher is the same as the stabilizing tank liquid of Example 1.

The processing steps, processing time, processing temperature and replenishment amount of the running processing were as follows.

The running process was performed until the bleach replenisher was replenished in an amount twice the bleach tank capacity. After the completion of the running process, the amount of residual silver in the highest density part was measured. However, the time from the color developing solution to the bleaching solution was 5 seconds.

Further, the bleaching solution after the running was stored for one week, and tar on the wall surface of the bleaching tank and sediment on the bottom were observed.

 Table 3 summarizes the results.

 The evaluation rank was as follows.

As is clear from Table 3, when the bromide concentration is high, the tar property and the precipitation property are inferior, and the desilvering property is also deteriorated.

Reference Example 4 The bleaching accelerator shown in Table 4 was added to the bleaching solution No. 12 of Reference Example 2 by 0.5.
The experiment was performed in the same manner as in Reference Example 2 except for adding g / addition.

 The results are summarized in Table 4.

From Table 4 above, it can be seen that the effect of the present invention is further promoted by using a specific bleaching accelerator in combination with the processing method of the present invention.

Example 1 A vinyl chloride nozzle having a diameter of 0.5 mm was installed in the bleaching treatment tank and the fixing treatment tank of Experiment No. 12 of Reference Example 2,
The experiment was carried out in the same manner as above while spraying a processing solution using an Iwaki magnet pump MD-15 on the emulsion surface of the photosensitive material.

As a result, the amount of residual silver was reduced from 1.0 mg to 0.6 mg per 100 cm ² .

Reference Example 5 Cyan coupler C'- used in Experiment No. 12 of Reference Example 2
Reference Example 2 except that C'-2 and C'-3 were replaced with cyan couplers shown in Table 5 having the same moles as C'-2 and C'-3.
The same processing and evaluation as described above were performed. Evaluation was also made of the case where the cyan coupler was replaced by the same amount (the same mole number) of C'-3 or CR-5.

Further, bleaching fog (cyan fog) was measured in addition to desilvering properties.

 The results are shown in Table 5.

From Table 5, it can be seen that the bleaching fog is significantly improved by using the preferred cyan coupler in the present invention. Regarding the desilvering property, by using a cyan coupler preferred in the present invention, the residual silver amount per 100 cm ^{2 is} 0.1 to 0.2.
mg was improved.

Reference Example 6 The same evaluation as in Reference Example 2 was carried out by adding 0.5 mol of ferric ammonium ethylenediaminetetraacetate to the bleaching solution Nos. 11 to 25 used in Reference Example 2, and the residual silver content per 100 cm ² was 0.02. ~ 0.03mg less.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shigeharu Koboshi 1 Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (56) References JP-A-1-260340 (JP, A) JP-A-59-229558 (JP, A) JP-A-62-250447 (JP, A) JP-A-59-111147 (JP, A) JP-A-62-250450 (JP, A)

Claims (1)

(57) [Claims] Claims: 1. Immediately after color development, processing with a bleaching solution is performed.
In a method for processing a silver halide color photographic light-sensitive material, which is subsequently processed with a processing solution having a fixing ability, the bleaching processing contains at least one selected from ferric complex salts of compounds represented by the following general formula [A]. And a bromide having a bromide concentration of 0.15 mol or more and 1.00 mol or less per bleach, and forcibly agitating the bleach and the processing solution having the fixing ability instead of the usual diffusion and transfer of the solution. A method for processing a silver halide color photographic light-sensitive material, characterized in that it is provided. General formula [A] Wherein A _{1 to} A ₄ may be the same or different, and
₂ OH, represents a -COOM or -PO ₃ M ₁ M _2. M, M ₁ and M ₂ each represent a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ]