JP2761884B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method excellent in silver bleaching power and excellent in processing solution stability and processing stability. The present invention relates to a method of processing a silver halide color photographic light-sensitive material capable of rapid processing (hereinafter, may be simply referred to as a "light-sensitive material").

[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.

Further, in a developing method in which a large amount of photosensitive material is continuously processed by an automatic developing machine or the like, in order to prevent the performance of the bleaching solution from deteriorating due to a change in the component concentration, the components of the processing solution are kept within a certain concentration range. Means are needed. In recent years, from the viewpoints of economy and pollution, a so-called concentrated low replenishment method in which these replenishers are concentrated and replenished in a small amount, or a method in which a regenerating agent is added to an overflow and used again as a replenisher has been proposed as such means. Is coming.

In particular, in the bleaching solution, a ferrous organic acid complex formed by bleaching the developed silver, for example, an iron (II) complex of ethylenediaminetetraacetate by ironing an iron (III) complex of ethylenediaminetetraacetate, that is, a ferric organic acid complex A method has been put to practical use in which a regenerating agent for supplementing the deficient components is further added by oxidizing and returning the solution, and then used again as a replenisher.

However, in recent years, so-called compact labs (also called mini-labs) have emerged in order to shorten the processing time of silver halide color photographic light-sensitive materials and to reduce the cost of collection and delivery. There is a high need for a reduction in the installation area of the machine, which requires complicated labor and management, and a regeneration process that requires a processing space is not preferable.

Therefore, a rich low replenishment method in which low replenishment is performed without performing regenerating processing is preferable.However, when the replenishment amount of the bleaching solution is extremely reduced, the concentration of the color developing solution component brought into the bleaching solution increases, and concentration by evaporation is performed. And the accumulation of color developing solution components is further increased. As described above, when the concentration of the color developing solution component in the bleaching solution increases, the mixing ratio of the color developing agent or the sulfite as a reducing component increases, the bleaching reaction is suppressed, and a failure such as so-called desilvering failure easily occurs. Become. In order to improve these disadvantages, a specific aminopolycarboxylic acid ferric complex salt described in Research Disclosure No. 24023 and JP-A No. 62-222252 and a mixture thereof are used. Technology has been proposed. However, it has been found that these techniques have various disadvantages. For example, the ferric complex of 1,3-propanediaminetetraacetic acid described in the above-mentioned literature or patent publication has an extremely strong oxidizing power and is suitable for rapid treatment, but stain is caused by the strong oxidizing power described above. It has been found that this is likely to occur. This stain becomes particularly noticeable when the color developing component is brought into the bleaching solution by running or when the bleaching solution is replenished at a low level. Furthermore, according to the results of our investigation, it was found that silver sludge is easily generated when 1,3-propanediaminetetraacetic acid ferric complex is used.

In recent years, minilabs have tended to perform anhydrous washing treatment (stabilization treatment) without using a so-called washing treatment in which the amount of washing water is greatly reduced by using a specific chemical. The stability of the processing solution tends to deteriorate. This tendency is increasingly emphasized in recent rapid processing.

[Object of the Invention] Accordingly, a first object of the present invention is to provide a method for processing a photographic material having excellent silver bleaching power and improved stability of a processing solution.

A second object of the present invention is to provide a method for processing a light-sensitive material which is excellent in processing stability and has improved precipitation during processing.

[Constitution of the Invention] The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, immediately after the color development processing, processing with a bleaching solution, followed by processing with a processing solution having a fixing ability. In the processing method, the bleaching solution is a processing solution containing a ferric complex salt of a compound represented by the following general formula [A] and a compound represented by the general formula [S-I] or [S-II], The present inventors have found that the above object can be achieved by applying forced liquid agitation to the step of processing with the bleaching solution and the step of processing with the processing solution having the fixing ability, and have accomplished the present invention.

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. ] In the formula, Z represents an atom group necessary for forming a heterocyclic ring.

In the formula [S-II] Q-SM 1 formula, Q is -SO ₃ M _2, -COOM _2, coupled directly or indirectly at least one selected from the group consisting of -OH and -NR ₁ R ₂ Represents a heterocyclic residue, M ₁ , M ₂ represents a hydrogen atom, an alkali metal, a quaternary ammonium, a quaternary phosphonium,
R ₁ and R ₂ represent a hydrogen atom or a substituted or unsubstituted alkyl group.

[Specific Configuration of the Invention] 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 the range of 0.002 mol to 0.5 mol, more preferably 0.01 mol to 0.45 mol, particularly preferably 0.05 mol to 0.4 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.

The bleaching solution according to the present invention contains a compound represented by the aforementioned general formula [SI] and / or [S-II] (hereinafter sometimes referred to as the compound of the present invention).

Hereinafter, specific examples of the compound represented by the general formula [SI] are shown. However, it is not limited to these.

Methods for synthesizing these compounds are well known,
Those skilled in the art can easily synthesize. These compounds can be referred to, for example, "New Experimental Chemistry Course Vol. 14" (Maruzen).

Specific examples of the heterocyclic residue represented by Q in the general formula [II] include an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a pentazole ring, Pyrimidine ring, thiadia ring, triazine ring,
A ring condensed with a thiadiazine ring or the like, or another carbon ring or a hetero ring, such as a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthooxazole ring, a triazaindolizine ring, and a diaza ring. And an indolizine ring and a tetraazaindolizine ring.

Preferred examples of the mercapto heterocyclic compound represented by the general formula [S-II] include those represented by the following general formula [S-III].

In the general formula [S-III], Y and Z each independently represent a nitrogen atom or CR ⁴ (R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group); R ³ is -SO ₃ M ² , -COOM ² , -OH and -NR
¹ R ² is an organic residue substituted with at least one selected from the group consisting of alkyl groups having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, hexyl, dodecyl) A octadecyl group), an aryl group having 6 to 20 carbon atoms (eg, a phenyl group, a naphthyl group, etc.), and L ¹ represents —S—, —O—, -CO -, - SO-, and -SO ₂ - shows a linking group selected from the group consisting of, n is 0 or 1.

These alkyl groups and aryl groups further include a halogen atom (F, Cl, Br, etc.), an alkoxy group (methoxy group, methoxyethoxy group, etc.), an aryloxy group (when R ² is an aryl group), and an aryl group (R ² is an alkyl group),
Amide group (acetamido group, benzoylamide group, etc.),
Carbamoyl group (unsubstituted carbamoyl group, phenylcarbamoyl group, methylcarbamoyl group, etc.), sulfonamide group (methanesulfonamide group, phenylsulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfo group) Famoyl group), sulfonyl group (methylsulfonyl group, phenylsulfonyl group, etc.), sulfinyl group (methylsulfinyl group, phenylsulfinyl group, etc.), cyano group, alkoxycarbonyl group (methoxycarbonyl group, etc.), allyloxycarbonyl group ( Phenoxycarbonyl group) and a nitro group.

Where the substituents of R ³ -SO ₃ M ² , -COOM ² , -OH and -NR ¹ R
^{When 2} is two or more, they may be the same or different.

M ¹ and M ² each mean the same thing as the general formula M ₁ and M ₂ described in [S-II].

Hereinafter, specific examples of the compound preferably used in the present invention will be shown.

The compound represented by the general formula [S-II] is known, and can be synthesized by a method described in the following literature.

That is, U.S. Patent Nos. 2,585,388 and 2,541,924,
No. 21842, JP-A-53-50169, British Patent 1,275,701,
DA Burgess et al., “Journal of Heterocyclic Chemistry” (DABerges et.al., “Journal
of Heterocyclic Chemistry ") Vol. 15, p. 981 (1978),
“The Chemistry of Heterocyclic Chemistry”, Imidazole and Derivatives, Part I
idazole and Derivatives partI), pp. 336-9, Chemical Abstract, 58 , 7921
(1963), p. 394, E. Hoggarth, "Journal of C.
Chemical Society "), 1160-7 (1949), and SR Saudler, W. Caro," Organic Functional.
Group Brevaration, Academic Press (SRSaudler, W. Karo, “Organic Fanctional Grou
p Preparation "Academic Press", pages 312-5, (196
8), M. Chamdon.et.al., Bulletin de la Societe Jimique de France (Bullet)
in de la Societe Chimique de France), p. 723 (195
4), DA Shirley, DW Array, “Journal of the American Chemical Society” (DASh
Irley, DWAlley, J. Amer. Chem. Soc., 79 , p. 4922 (1954), A. Ball, W. Marchwald, Berichte (A.
Wohl, W. Marchwald, Ber.) (German Chemistry Journal), Volume 22, 5
P. 68 (1889), "Journal of American Chemical Society" (J. Amer. Chem. Soc.) 44 , 1502-10
Page, U.S. Patent No. 3,017,270, UK Patent No. 940,169, Tokubo Sho
49-8334, JP-A-55-59463, Advanced in Heterochemistry
9 , 165-209 (1968), West German Patent 2,716,707, The Chemistry of Heterocyclic Compound, The Chemistry of Heterocyclic Compound
s, Imidazole and Derivatives), Vol I, page 384, Organic Synthesis (Org. Synth.) IV., page 569, (196
3), Berichte (Ber.), 9 , p. 465 (1976), "Journal of the American Chemical Society"
(J. Amer. Chem. Soc.) 45 , p. 239 (1923), JP-A-50-8
No. 9034, No. 53-28426, No. 55-21007, Japanese Patent Publication No. 40-28
No. 496, etc.

When the compound of the present invention is used by being contained in a bleaching solution, it is generally 0.5 mg to 20 g per bleaching solution, but it is particularly preferable to add 1 mg to 5 g per bleaching solution.

When the bleaching solution according to the present invention contains at least one of imidazole and derivatives thereof as described below or a compound represented by the following general formulas [I] to [IX], the bleaching solution exhibits a desired effect of the present invention more favorably. In addition, since the bleaching solution has another effect of improving the precipitation caused by silver in the bleaching solution, it is more preferably used in the present invention.

[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. ] Wherein R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 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. Represent.

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, and R ″ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (where a 5- to 6-membered unsaturated ring is condensed, Or an amino group, n _{1 to} n ₆ and m ₁ to
m ₅ each represent an integer of 1-6.

B represents an alkylene group having 1 to 6 carbon atoms, Y is -N, Or represents -CH, 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.

The compound represented by the formula also includes an ethanolated compound and a salt thereof. ] [Wherein, R ₆ and R ₇ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or- Represents B ₁ -S-Z ₁ . However, R ₆ and R ₇ may combine to form a ring. Y ₁ is N- or CH-
And B ₁ represents an alkylene group having 1 to 6 carbon atoms,
Z ₁ is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue or n ₇ represents an integer of 1-6. ] Wherein R ₈ and R ₉ are each The stands, R ₁₀ is alkyl or - represents a _{(CH 2) n 8 SO 3} .
(Wherein R ₁₀ is -. (When _{CH 2) n 8 SO 3,} l represents 0, it represents a case of the alkyl group) G represents an anion. n ₈
Represents an integer of 1 to 6. ] [In the formula, Q ₁ represents an atom group necessary to form a nitrogen-containing heterocyclic ring (including a condensed 5- or 6-membered unsaturated ring or saturated ring), and R ₁₁ represents a hydrogen atom, an alkali Metal atom, Or an alkyl group. However, Q 'has the same meaning as that of Q _1. ] [Wherein, D ₁ , D ₂ , D ₃ and D ₄ each represent a mere bond, an alkylene group having 1 to 8 carbon atoms or a vinylene group, and q ₁ , q ₂ , q ₃ and q ₄ each represent 0 , 1 or 2. The ring formed together with the sulfur atom is further 5 to 6
It may be fused to a membered saturated or unsaturated ring. ] [Wherein X ₂ is -COOM ', -H, -OH, -SO ₃ M', -CON
_{H 2, -SO 2 NH 2,} -NH 2, -SH, -CN, -CO 2 R 16, -SO
₂ R ₁₆ , -OR ₁₆ , -NR ₁₆ R ₁₇ , -SR ₁₆ , -SO ₃ R ₁₆ , -NHCOR
₁₆ , —NHSO ₂ R ₁₆ , —OCOR ₁₆ or —SO ₂ R ₁₆ , wherein Y ₂ is Or m represents a hydrogen atom, and m ₉ and n ₉ each represent an integer of 1 to 10. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ and R ₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or R ₁₆ represents a lower alkyl group, R ₁₉ represents -NR
_{20 represents} R ₂₁ , -OR ₂₂ or -SR ₂₂ , R ₂₀ and R ₂₁ each represent a hydrogen atom or a lower alkyl group, and R ₂₂ represents an atom group necessary for bonding with R ₁₈ to form a ring. Represent. R ₂₀ or R ₂₁
May combine with R ₁₈ to form a ring. M 'represents a hydrogen atom or a cation. ] In the formula, Ar is a divalent aryl group or a combination of an aryl group and an oxygen atom and / or an alkylene group.
B ₂ and B ₃ each represent a lower alkylene group; R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydroxy-substituted lower alkylene group; and x and y each represent 0 or 1. Represent. G ′ represents an anion, and z is 0, 1 or 2
Represents ] Wherein R ₂₉ and R ₃₀ are each a hydrogen atom, an alkyl group,
R ₃₁ represents a hydrogen atom or an alkyl group; R ₃₂ represents a hydrogen atom or a carboxy group; The compounds represented by the general formulas [I] to [IX] or imidazole and derivatives thereof as described below, which are preferably used in the present invention, are compounds generally used as a bleaching accelerator. That.

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.

(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,
Exemplified compounds Nos. I-2, I-4 to 7, I-9 to 13, I-16 to 21, I-2 described on pages 51 to 115 of JP-A-263568.
3, 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 5
5, II-57-60, II-62-64, II-67-71, II-73-7
9, II-81 to 84, II-86 to 99, II-101,102, II-104 to 1
10, II-112 to 119, II-121 to 124, II-126, II-128 to
144, II-146, II-148 to 155, II-157, III-4, III
-6 to 8, III-10, 11, III-13, III-15 to 18, III-2
0, III-22, III-23, III-25, III-27, III-29-3
2, III-35, 36, IV-3, IV-4, V-3 to 6, V-8
~ 14, V-16 ~ 38, V-40 ~ 42, V-44 ~ 46, V-48 ~
66, V-68-70, V-72-74, V-76-79, V-81,8
2, V-84-100, V-102-108, V-110, V-112,11
3, V-116 to 119, V-121 to 123, V-125 to 130, V-1
32-144, V-146-162, V-164-174, V-176-18
4, VI-4, VI-7, VI-10, VI-12, VI-13, VI-1
6, VI-19, VI-21, VI-22, VI-25, VI-27 to 34, VI
-36, VII-3, VII-6, VII-13, VII-19, VII-20
And exemplified compounds (III-2) to (III-3), (III-) described in pages 22 to 25 of JP-A-63-17445.
5) to (III-10), (III-12) to (III-45), (III
-47) to (III-50), (III-52) to (III-54), (I
Compounds such as II-56) to (III-63) and (III-65) can be used in the same manner.

These bleaching accelerators may be used alone or two or more of them may be used in combination.
Good results are obtained in the range of 0.01 to 100 g. However,
In general, when the amount is too small, the effect of accelerating bleaching is small, and when the amount is too large, precipitation may occur to contaminate the photosensitive material to be processed.
The amount is preferably 0.05 to 50 g, more preferably 0.05 to 15 g per bleaching solution.

The general formulas [SI] to [S-II] and [I] to [IX]
When the compound represented is added to the bleaching solution, it may be added and dissolved as it is, but it is common to add it by dissolving it in water, alkali, an organic acid or the like in advance, and if necessary, methanol, It can also be dissolved and added using an organic solvent such as ethanol or acetone.

The processing temperature of the bleaching solution of the present invention is used at 20 ° C to 45 ° C, preferably 25 ° C to 42 ° C.

In the bleaching solution of the present invention, a halide such as ammonium bromide is usually added and used. However, in the present invention, the concentration of the commonly used halide is reduced because the bleaching agent of the present invention has a strong oxidizing power. It is possible to make the concentration.

By lowering the halide concentration, there are effects such as enrichment of the kit and prevention of precipitation of the oxidizing agent. Another effect is that silver sludge is hardly generated.

The halide used in the present invention includes ammonium chloride, sodium chloride, potassium chloride, ammonium bromide, sodium bromide, and potassium bromide, and is preferably ammonium chloride or ammonium bromide.
In particular, ammonium bromide has a great effect of promoting bleaching,
It is preferably used.

The halide concentration is 0.05 to 3 mol per bleaching solution,
Preferably it is 0.10 to 2.0 mol, particularly preferably 0.15 to 1.5 mol.

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.

In order to achieve the object of the present invention with high efficiency, the bleaching solution of the present invention preferably contains a buffer, particularly a "buffer having a buffering ability at pH 3 to 7". The K ₂ CO ₃ is needed the addition of more than 5 g / l in order to pH7 the pH value of the aqueous solution from pH3 containing a certain amount of buffering agent and "buffering agent having a buffering capacity in pH3~7" according Refers to buffer. As the buffer preferably used, the following general formula [XI], [XII] or [XII]
And inorganic compounds such as compounds containing at least one nitrogen, phosphorus or boron atom.

General formula [XI] A-COOH In the formula, A represents a hydrogen atom or an organic compound group.

In the formula [XII] B-PO ₃ H ₂ , B represents a hydrogen atom or an organic compound group.

In the formula, C ′, D, and E each represent a hydrogen atom or an organic compound group. However, at least one of C ', D and E is an organic compound group.

Next, specific examples of the buffer preferably used in the present invention will be described.

Preferred compounds as fatty acids are acrylic acid, adipic acid, acetylenedicarboxylic acid, acetoacetic acid, azelaic acid, isocrotonic acid, isopropylmalonic acid, isobutyric acid, itaconic acid, isovaleric acid, ethylmalonic acid, caproic acid, formic acid, valeric acid , Citric acid, glycolic acid, glutaric acid, crotonic acid, chlorofumaric acid, α-chloropropionic acid, gluconic acid, glyceric acid, β-chloropropionic acid, succinic acid, cyanoacetic acid, diethylacetic acid, diethylmalonic acid, dichloroacetic acid, Citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, meso-tartaric acid, trichlorolactic acid, tricarballylic acid, trimethylacetic acid, lactic acid,
Vinyl acetic acid, pimelic acid, pyrotartaric acid, grape acid, fumaric acid, propionic acid, propylmalonic acid, maleic acid,
Malonic acid, mesaconic acid, methylmalonic acid, monochloroacetic acid, n-butyric acid, malic acid, aspartic acid, DL-alanine, glutamic acid, 3,3-dimethyl-glutaric acid and the like.

Preferred compounds having an acid having a cyclic structure include ascorbic acid, atropeic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (m-, p-), and chlorobenzoic acid (o-, m-, p-). ), Chlorophenylacetic acid (o-, m
-, P-), cinnamic acid, salicylic acid, dioxybenzoic acid (2,3,2,4,2,5,2,6,3,4,3,5), cyclobutane-1,
1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid (Trans-, Cis-), cyclopropane-1,1-dicarboxylic acid, cyclopropane-1,2-dicarboxylic acid (Trans-,
Cis-), cyclohexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (Trans-, Cis-), cyclohexylacetic acid, cyclopentane-1,1-dicarboxylic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrophenol diphenyl acid, sulfanilic acid, terephthalic acid, toluic acid (o-, m-, p-), naphthoic acid (α-, β
-), Nicotinic acid, nitroanisole (o-, m-, p
-), Nitrobenzoic acid, nitrophenylic acid (o-, m
-, P-), p-nitrophenetol, pyromucoic acid, uric acid, hippuric acid, barbituric acid, picolinic acid boronic acid, phenylacetic acid, phenylic acid, phthalic acid, fluorobenzoic acid (o-, m-, p- ), Bromobenzoic acid (o-, m-,
p-), hexahydrobenzoic acid, benzylic acid, dl-madelic acid, meditylenic acid, methoxybenzoic acid (o-, m-,
p-), methoxycinnamic acid (o-, m-, p-), p-
Methoxyphenylacetic acid, gallic acid, aminobenzoic acid (o
-, M-, p-) and the like.

Preferred compounds as amine compounds are isoamylamine, isobutylamine, isopropylamine, ethylamine, ethylenediamine, diisoamylamine, diisobutylamine, diethylamine, diethylenetriamine, dipropylamine, dimethylamine, tetraethylenepentamine, tetramethylenediamine, triethylamine, Trimethylamine, trimethyldiamine, m
-Butylamine, sec-butylamine, tert-butylamine, m-propylamine, pentamethylenediamine,
Hexamethylenetetramine, quinoline, o-toluidine, aminobenzenesulfonic acid (o-, m-, p-),
N-methylbenzylamine, methylbenzylamine (o
-, M-, p-), 2-methylpiperidine, N-methoxybenzylamine, methoxybenzylamine (o-, m-
-, P-), benzylamine, coniine, diethylbenzylamine, cyclohexylamine, piperazine and the like.

Preferred inorganic acids include nitrous acid, phosphorous acid, hypophosphorous acid, boric acid, phosphoric acid, pyrophosphoric acid, triphosphoric acid, metatriphosphoric acid, polyphosphoric acid, polymetaphosphoric acid, and the like.

Preferred compounds among other organic compounds are N- (2-
Acetamido) iminodiacetic acid, N- (2-acetamido) -2-aminoethanesulfonic acid, bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane, 2- (N-morpholino) ethanesulfonic acid, 3-
(N-monophorino) -2-hydroxypropanesulfonic acid, piperazine-N, N'-bis (2-ethanesulfonic acid), ethylenediaminediacetic acid, ethylenediamine-2
-Propionic acid, β-aminoethyliminodiacetic acid and the like, and other preferable organic phosphoric acids include aminomethylphosphonic acid-N, N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1 , 2,4-tricarboxylic acid, and the following (P-1) to (P-34).

Among them, more preferably, fatty acids, acids having a cyclic structure,
Amine compounds and inorganic salts are preferable, and fatty acids and amino compounds are particularly preferable.

In addition, among organic acids, acetic acid is slightly inferior in effect to the above compounds.

However, at least 40% (molar ratio), preferably at least 50% (molar ratio) of the ferric aminopolycarboxylate (or phosphonic acid) complex salt contained as a bleaching agent is the second compound of the compound represented by the general formula [A]. When it is an iron complex salt or when the ferric complex salt of the compound represented by the general formula [A] is 0.2 mol / l or more, the acetic acid content is high in the range of 0.5 to 3 mol / l, preferably 0.8 to 3 mol / l. It has been found that in the range of 22 mol / l, it is extremely effective for liquid stability (effect of preventing suspended matter).

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 respectively 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, and are preferably represented by the following general formula [XX
I] and [XXII].

Wherein, E is a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene _{group, -R 83 OR 83 OP 83 -} , - R 83
ZR ₈₃ - represents, Z is> NR ₈₃ -A _6, represents> N-A _6, R ₇₉
~ R ₈₃ represents a substituted or unsubstituted alkylene group, and A ₂ -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 [XXI] and [XXII] are shown below.

[Exemplified Compound] [XXI-1] Ethylenediaminetetraacetic acid [XXI-2] Diethylenetriaminepentaacetic acid [XXI-3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetic acid [XXI-4] ] 1,3-propylenediaminetetraacetic acid [XXI-5] triethylenetetraminehexaacetic acid [XXI-6] cyclohexanediaminetetraacetic acid [XXI-7] 1,2-diaminopropanetetraacetic acid [XXI-8] 1,3- Diaminopropan-2-ol-tetraacetic acid [XXI-9] ethyl ether diamine tetraacetic acid [XXI-10] glycol ether diamine tetraacetic acid [XXI-11] ethylenediamine tetrapropionic acid [XXI-12] phenylenediamine tetraacetic acid [XXI- 13] Ethylenediaminetetraacetic acid disodium salt [XXI-14] Ethylenediaminetetraacetic acid tetra (trimethyla Ammonium salt) [XXI-15] Ethylenediaminetetraacetic acid tetrasodium salt [XXI-16] Diethylenetriaminepentaacetic acid pentasodium salt [XXI-17] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-tri Sodium acetate sodium salt [XXI-18] Propylenediaminetetraacetic acid sodium salt [XXI-19] Ethylenediaminetetramethylenephosphonic acid [XXI-20] Cyclohexanediaminetetraacetic acid sodium salt [XXI-21] Diethylenetriaminepentamethylenephosphonic acid [XXI-22] ] Cyclohexanediaminetetramethylenephosphonic acid [XXII-1] Nitrilotriacetic acid [XXII-2] Methyliminodiacetic acid [XXII-3] Hydroxyethyliminodiacetic acid [XXII-4] Nitrilotripropionic acid [XXII-5] Nitrotrimethylenephosphonic acid [ XXII-6] Iminozi Methylenephosphonic acid [XXII-7] hydroxyethyliminodimethylenephonic acid [XXII-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. (XXI-1), (XXI-2), (XXI-
4), (XXI-6), (XXI-7), (XXI-10), (XXI
-19), (XXII-1) and (XXII-5). Among these, (XXI-4) is particularly preferred from the viewpoint of the effects 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 replenishment rate of the bleaching solution according to the present invention is to not 50ml per silver halide color photographic light-sensitive material 1 m ² 250 ml are preferred.

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; Ammonium sulfate is preferred as a fixing agent, and is preferably used.

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.

When the fixing solution and the bleach-fixing solution according to the present invention contain 0.1 g / l to 10 g / l of iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.), Further promote the effects of the invention. In particular, 0.3 g / l to 5 g / l, especially especially 0.5 g / l to 3 g / l, most preferably 0.8 g / l to 2 g / l
With good results.

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.

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, The range is preferably from mol / l to 0.65 mol / l, particularly preferably from 0.15 mol / l to 0.50 mol / l. Particularly preferred is a range of 0.20 mol / l to 0.40 mol / l.
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, forcible liquid stirring is applied to the bleaching solution, the fixing solution and the bleach-fixing solution. The reason for this is not only that the effects of the present invention can be achieved more favorably, but also that rapid processing is appropriate.

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 impact force of the spray is mainly determined by the flow rate (l / 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 air volume is 2 liters per rack of the automatic processor.
From 30 / min to 30 l / min is required, and more preferable results are obtained from 5 to 20 l / min. 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 the side wall in the processing liquid tank of the automatic developing machine and the photosensitive material is irradiated with ultrasonic waves to increase the development promotion efficiency. . 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.

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.

Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution according to the present invention flows into the bleaching solution in the subsequent step. This is because when a certain amount of the color developing solution according to the present invention flows into the bleaching solution, the generation of sludge in the bleaching solution is improved.

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 second encore, hydroxamic acid, bentose or Hexose, progalol-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 method of treating with the bleaching solution of the present invention and immediately treating with a fixing solution or a bleach-fixing solution followed by a stabilizing solution is preferred from the viewpoint of the effects of the present invention, particularly in terms of rapidity, but further effects. In addition, there is an effect that the stability of the processing liquid (stabilizing liquid) is improved.

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 processor, the transport method, the squeeze method on the surface of the photosensitive material, etc. In the case of a color photosensitive material for photographing, in the case of a normal color film (roll film), the carry-in amount is usually 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 ~4.0l / m 2} , the effect is particularly noticeable replenishment rate 200ml / m ² ~ 1500ml / m
It is in the range of ² .

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.

(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 , R _{1 to} R ₃ each represent an alkylene group. A ₁ to A ₃ each represent 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. ) (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.) (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 is a hydrogen atom, a hydroxyl group, -COOM, -PO ₃ M ₂ or J represents a hydrogen atom, an alkyl group, a -C ₂ H ₄ OH or -PO ₃ M _2. M represents a hydrogen atom or an alkali metal atom;
And m represent 0 or 1, respectively.

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.

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.

Further, the pH value of the stabilizing solution preferably used in the present invention, in addition to the effects of the present invention, is preferably in the range of pH 4.0 to 9.0 for the purpose of improving image storability, more preferably pH 4.5.
~ 9.0, particularly preferably pH 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.

The quaternary ammonium compounds include, specifically, benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts and the like.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. Examples thereof include 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)
As long as Ca or Mg ions are reduced to 5 ppm or less, any treatment may be used. For example, treatment with an ion exchange resin or a reverse osmosis membrane is preferably used alone or in combination. Published technical report 87 on ion exchange resins and reverse osmosis membranes
No. 1984, 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 described in West German Patent 2,331,220), ion exchange method (described in JP-A-51-17114, German Patent 2,548,237), and metal replacement method (described in German Patent 2,548,237). British Patent 1,353,805) 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, the induction ratio of the washing water after the treatment is 50 μs / cm or less, and 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].

(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. ) 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 group (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.), oxycarbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (eg, acetyl, benzoyl, etc.), heterocycle (For example, pyridyl group, prazolyl group, etc.), alkoxy group, aryloxy group, acyloxy group and the like.

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. Preferably, it is 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.), a 5-membered or 6-membered heterocyclic group and the like can be mentioned.

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.

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, 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].

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; Amide 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.

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.

R ₂ is a hydrogen atom bonded to NH directly or through NH, CO or SO ₂ ; an aliphatic group having 1 to 30 carbon atoms;
30 aromatic group, a heterocyclic group having 1 to 30 carbon atoms, -OR _8, -C
OR 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 , R ₅
And R ₆ are the same as defined above, and 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. I can list this R ₃
Preferably contains 0 to 30 carbon atoms. 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 × 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.

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, it is possible to provide a processing solution having excellent silver bleaching power and improved stability of the processing solution, and has excellent processing stability and improved generation of precipitate during processing. And a method for processing the light-sensitive material.

[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 all examples, the amount of silver halide photographic light-sensitive material is particularly shows the g per 1 m ² unless otherwise noted.
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 0.25 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored coupler (CM-2) 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 (E _m -1) ... 1.0 silver iodobromide emulsion (E _m -2) ... 0.5 sensitizing dye (S-1) ... 2.5 × 10 ^-4 (Mol / silver 1 mol) Sensitizing dye (S-2) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.5 × 10 ^-4 (mol / silver 1 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 solvent (oil-1) ... 0 .5 Gelatin ... 1.4 Layer 4: High Sensitivity Red-sensitive emulsion layer (RH) Silver iodobromide emulsion (E _m -3) ... 2.0 Sensitizing dye (S-1) ... 2.0 × 10 -4 ( mol / silver
Mol) Sensitizing dye (S-2) ... 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) ... 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) ) '... 0.15 Cyan coupler (C-2)' ... 0.018 Cyan coupler (C-3) '... 1.15 Colored cyan coupler (CC-1) ... 0.015 DIR compound (D-2) ... 0.05 High boiling solvent (oil-1) 0.5 gelatin: 1.4 Fifth layer: intermediate layer (IL-2) Gelatin: 0.5 sixth layer: low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (E _m -1): 1.0 sensitizing dye ( S-4) 5.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 1.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.5 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 1.0 7th layer: Intermediate layer (IL- ) Gelatin ... 0.8 High-boiling solvent (oil-1) ... 0.2 8th layer: high sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (E _m -3) ... 1.3 Sensitizing dye (S-6) ... 1.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) ... 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) ... 0.5 × 10 ^-4 (mol / 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 solvent (oil-3): 0.1 Gelatin: 0.8 Tenth layer: Low sensitivity blue sensitivity emulsion layer (BL) silver iodobromide emulsion (E _m -1) ... 0.25 silver iodobromide emulsion (E _m -2) ... 0.25 sensitizing dye (S-10) ... 7.0 × 10 -4 ( mol / silver Mol) Ye -Coupler (Y-1) ... 0.6 yellow coupler (Y-2) ... 0.12 DIR compound (D-2) ... 0.01 high boiling point solvent (oil-3) ... 0.15 gelatin ... 1.0 11th layer: high-sensitivity blue-sensitive emulsion layer ( BH) silver iodobromide emulsion (E _m -4) ... 0.50 silver iodobromide emulsion (E _m -1) ... 0.20 sensitizing dye (S-9) ... 1.0 × 10 -4 ( mol / 1 mol of silver), up 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 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 point solvent (oil-1) ... 0.1 High boiling point solvent (oil-4) ... 0.1 Formalin scavenger (HS-1) ... 0.5 Formalin scavenger (HS-2) 0.2 Gelatin ... 1.0 13th layer: 2nd protective layer (Pro-2) Surfactant (Su-1) ... 0.005 Alkali-soluble matting agent (average particle size 2 m) ... 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, and a hardening layer. Agents H-1 and H-2, preservative DI-
1. Stabilizer Stab-1 and antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.50 μm, average silver iodide content 7.7% Monodisperse surface low silver iodide content emulsion Em-2 Average grain size 0.35 μm, average silver iodide content 2.2% Monodisperse Emulsion with uniform composition Em-3 Average grain size 0.81 μm, average silver iodide content 6.0% Monodisperse surface-low silver iodide-containing emulsion Em-4 Average grain size 0.93 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 and JP-A-60-138538.
-With a multilayer structure adjusted with reference to each publication of No. 245151,
A silver iodobromide emulsion mainly composed of octahedrons.

Em-1 to Em-4 all had an average value of the particle diameter / particle thickness of 1.1, and the width of the particle distribution was 1 respectively.
4, 10, 12 and 12%.

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

<Experimental processing> Processing process Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38 ° C Bleaching (1 tank) 45 seconds 38 ° C Fixing (1 tank) 1 minute 45 seconds 38 ° C Stabilization (3 tank cascade) 1 minute 38 ° C drying (40 ° C to 80 ° C) 45 seconds The treatment liquid composition used is as follows.

[Color developing 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 solution] Ferric organic acid complex salt described in Table 1 Disodium ethylenediamineacetate 2 g Ammonium bromide 150 g Glacial acetic acid 10 ml Compound of the present invention described in Table 1 Ammonium nitrate 30 g Add water to make 1 and use ammonia water or glacial acetic acid Adjust to pH 5.8.

[Fixing solution] Ammonium thiosulfate 150 g Ammonium sulfite 20 g Disodium ethylenediaminetetraacetate 0.5 g Sodium carbonate 10 g Add water to make 1 and adjust the pH with acetic acid and aqueous ammonia.
Adjust to 7.0.

[Stabilizing liquid] formaldehyde (37% solution) 1 ml 5-chloro-2-methyl-4-isothiazolin-3-one 0.05 g emulgen 810 1 ml sodium formaldehyde bisulfite adduct 2 g hexamethylenetetramine 0.5 g With ammonia water and 50% sulfuric acid
The pH was adjusted to 7.0.

As shown in Table 1 below, an experiment was conducted using the ferric organic acid complex salt of the bleaching solution and the compound of the present invention.

The cyan stain of the unexposed portion of the processed film sample was measured as a typical characteristic of bleach fog using a photoelectric densitometer PDA-65A (manufactured by Konica Corporation).

Further, the amount of residual silver in the highest density part was measured by a fluorescent X-ray method.

 The results are shown in Table 1 below.

In the table, EDTA.Fe is ferric ammonium salt of ethylenediaminetetraacetic acid, (A-1) .Fe, (A-2) .Fe, (A
-4) .Fe and (A-7) .Fe are (A-1) and
It means the ferric ammonium salt of (A-2), (A-4) or (A-7). Hereinafter, it is synonymous.

As is clear from Table 1 above, the use of the ferric organic acid complex salt of the present invention allows the desilvering reaction to be carried out quickly and the processability to be increased. However, it has a drawback of high bleaching fog, and it can be seen that the use of the compound of the present invention significantly improves the use.

Reference Example 2 Using Experiment No. 1-5 of Reference Example 1, a buffer was added to the bleaching solution to adjust the pH to the amount shown in Table 2, and then the same treatment as in Reference Example 1 was performed. Was evaluated.

 The results are shown in Table 2.

As is clear from Table 2, the addition of acetic acid as a buffer to the bleaching solution reduces the bleaching stain, and the addition of 0.5 mol or more, particularly 0.8 mol or more, improves the bleaching stain more remarkably. The addition of the preferred buffering agent of the present invention other than acetic acid has also greatly improved the bleaching stain.

Reference Example 3 An experiment was carried out in the same manner as in Reference Example 1 except that 1.5 g / l of a bleaching accelerator shown in Table 3 was added to the bleaching solution obtained in Experiment No. 1-5 of Reference Example 1.

The residual silver amount and the unexposed portion of the cyan stain of the processed film sample were measured.

 Table 3 summarizes the results.

Table 3 shows that the use of a specific accelerator in combination with the bleaching solution of the present invention further enhances the suitability for rapid processing and at the same time improves the cyan stain.

Example 4 A running process was performed using the color negative film and the processing solution prepared in Experiment Nos. 1-4 of Reference Example 4 and the following replenishers.

 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.

[Bleaching replenisher] Ferric organic acid complex salt (described in Table 4) 0.4 mol Disodium ethylenediamineacetate 2 g Ammonium bromide 178 g Glacial acetic acid 21 ml Ammonium nitrate 35 g Water was added to pH 1, and the pH was adjusted to 5.6 with aqueous ammonia or glacial acetic acid. Adjust to

[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 the pH to 6.5.

 As the stabilizing replenisher, the stabilizing solution of Reference Example 1 was used.

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

The running process takes 40 days to reduce the bleach tank capacity to 2
This was done until twice the amount of bleach replenisher was replenished. The film sample after the running treatment was evaluated in the same manner as in Reference Example 1, and the bleaching stain and the amount of residual silver in the highest density part were measured.

After standing for 3 days after the completion of the running treatment, the precipitation in the bleaching solution tank was observed.

The observation of the sedimentation was evaluated by looking at the bottom in the tank as shown below.

○ No precipitation △ Some precipitation was observed × A large amount of precipitation Then, the same experiment was performed by replacing the ferric organic acid complex in the bleaching solution and the bleach replenisher with the organic acid iron complex shown in Table 4 below. .

 The results are summarized in Table 4.

As can be seen from Table 4, the bleach of the present invention has suitability for rapid processing. However, there is a drawback that bleaching stain is easily generated and sludge is easily generated.
It can be seen that the above problems are greatly improved by using the compound of the present invention.

Reference Example 5 Cyan coupler (C) used in Experiment Nos. 1-10 of Reference Example 1
The same processing as in Reference Example 1 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)'. As a result of the evaluation, almost the same results were obtained.

However, bleaching fog (cyan fogging) was also measured.

 The results are shown in Table 5.

As is evident from Table 5, bleaching fog is reduced by changing the cyan coupler to a cyan coupler preferable for the present invention.

Example 1 In the bleaching processing tank and the fixing processing tank of Experiment Nos. (1-5) to (1-10) of Reference Example 1, a nozzle made of vinyl chloride having a diameter of 0.5 mm was installed, and the photosensitive material emulsion surface was illuminated. The experiment was carried out in the same manner as above while spraying the treatment liquid using the magnet pump MD-15.

As a result, each of the cyan stains was reduced by 0.01 to 0.02, and the amount of residual silver was reduced by half.

Reference Example 6 The stable liquid (first tank) after running of Reference Example 4 was 30 ° C.
For 2 weeks, and the appearance of the liquid after storage was evaluated.

○ Pear sulfide △ Slight sulfide × Ali sulfide As is evident from Table 6, the use of the organic acid ferric complex salt of the present invention increases the storage stability of the stable solution as compared with EDTA • Fe.

Claims (1)

(57) [Claims] In a method for processing a silver halide color photographic light-sensitive material, the bleaching solution is processed immediately after a color developing process by a bleaching solution and subsequently processed by a processing solution having a fixing ability. A processing solution containing a ferric complex salt of a compound represented by the general formula [SI] or a compound represented by the general formula [S-II], and a step of treating with the bleaching solution and having the fixing ability. A method for processing a silver halide color photographic light-sensitive material, wherein forcible liquid stirring is applied to the step of processing with a processing liquid. 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. ] In the formula, Z represents an atom group necessary for forming a heterocyclic ring. In the formula [S-II] Q-SM 1 formula, Q is -SO ₃ M _2, -COOM _2, coupled directly or indirectly at least one selected from the group consisting of -OH and -NR ₁ R ₂ Represents a heterocyclic residue, M ₁ , M ₂ represents a hydrogen atom, an alkali metal, a quaternary ammonium, a quaternary phosphonium, R ₁ ,
R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group.