JP2607072B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material having a rapid silver bleaching ability.

BACKGROUND OF THE INVENTION A recent trend is to shift from a centralized processing type in which the demand in the market is processed by a few large labs to a distributed processing type in which processing is performed by a large number of small labs. In such small laboratories, there is an increasing demand for a more compact processing machine and at the same time, a faster processing that can respond to short-time service. In particular, high-sensitivity silver halide color photographic light-sensitive materials for photography require a long processing time, and in order to reduce the time from receiving a color negative film that has already been shot at the window to handing over the print to the customer, use a color negative film. It is absolutely necessary to reduce the processing time. Above all, the desilvering step occupies nearly half of the total processing time, and speeding up the desilvering step is an important issue.

In order to speed up the desilvering step, for example, a method has been proposed in which various bleaching accelerators are added to a bleaching bath, a bleach-fixing bath, or a prebath thereof.

Bleach accelerators include, for example, U.S. Pat.
No., British Patent No. 1,138,842, JP-A-53-141623, 5
4-52534, various mercapto compounds described in JP-A-53-95631, etc., compounds having a disulfide bond described in JP-A-53-9630, thiazolidine derivatives described in JP-B-53-9854, Isothiourea derivatives described in JP-A-53-94927, thiourea derivatives described in JP-B Nos. 45-8506 and 49-26586, thioamide compounds described in JP-A-49-42349, The dithiocarbamates described in No. 26506 are known.

Some of these bleaching accelerators certainly have a bleaching promoting effect, but the effect is not always sufficient,
In particular, when the color developing solution is mixed into the bleaching solution or the bleach-fixing solution, not only the accelerating effect is remarkably reduced, but also the use of such a bleaching accelerator tends to promote so-called poor recoloring due to leuco of the cyan dye. It has been clarified that such poor recoloring becomes more remarkable when the color developing solution is mixed into the bleaching solution or the bleach-fixing solution.

Accordingly, there is a demand for a method for processing a silver halide color photographic light-sensitive material that can speed up the desilvering step of the silver halide color photographic light-sensitive material and does not deteriorate the reproducibility of the cyan dye.

[Object of the Invention] An object of the present invention is to provide a processing method using a processing solution which enables rapid processing of a silver halide color photographic light-sensitive material and has a bleaching ability with extremely little deterioration in recoloring property of a cyan dye. is there.

[Constitution of the Invention] The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, after imagewise exposing the same to at least a color developing solution and a bleaching ability. A silver halide color photographic light-sensitive material, wherein the silver halide emulsion layer contains silver halide grains having a silver iodide content of 0.5 mol% or more. As a color developing solution, a photographic light-sensitive material contains at least one of the compounds represented by the following general formula [A], and as a processing solution having a bleaching ability,
It contains at least one compound selected from the compounds represented by the following general formulas [I] to [IX], and the mixing ratio of the color developing solution into the processing solution having the bleaching ability is 5% or more. This was achieved by a method for processing a silver halide color photographic light-sensitive material characterized by the following.

General formula [A] In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

General formula [I] In the formula, Q represents a group of atoms 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 6 carbon atoms. Alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups (5-
A 6-membered unsaturated ring is condensed) or an amino group.

General formula [II] In the formula, R ₂ and R ₃ are each a hydrogen atom and a carbon atom 1
Represents an alkyl group, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group. A is Or n ₁ monovalent heterocyclic residue represents the (5-6 membered unsaturated ring including those condensed), X is = S, = O or =
NR ″, wherein R and R ′ are the same as R ₂ and R ₃ respectively, X ′ is the same as X, and Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, or 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, and n ₁
~n ₆ and m ₁ ~m ₅ each represents an integer of 1-6. B
Represents an alkylene group having 1 to 6 carbon atoms, and Y represents -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 are each -B-
May represent 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 enol compound and a salt thereof.

General formula [III] In the formula, R ₆ and R ₇ are each a hydrogen atom and a carbon atom 1
6 alkyl group, hydroxy group, carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B ₁ -S-Z _1. However, R ₆ and R ₇ may combine to form a ring. Y ₁ is N- or CH-
Represents B ₁ represents an alkylene group having 1 to 6 carbon atoms, Z ₁ represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue or Represents n ₇ is an integer of 1-6.

General formula [IV] Where R₈And R₉Are eachOrAnd R_TenIs an alkyl group or-(CH_Two)_n8SO_Three Represents (However, R_TenIs-(CH_Two)_n8
SO_Three In the formula, l represents 0, and when it is an alkyl group, 1 represents
Express. ) G Represents an anion. n₈Is an integer from 1 to 6
Represents

General formula [V] In the formula, Q ₁ represents an atom group necessary for forming 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.

General formula [VI] Wherein D ₁ , D ₂ , D ₃ and D ₄ are each a mere bond,
Represents an alkylene group or a vinylene group having 1 to 8 carbon atoms, each q _1, q _2, q ₃ and q ₄ represent 0, 1 or 2. Further, the ring formed together with the sulfur atom is further 5 to
Six-membered saturated or unsaturated rings may be fused.

General formula [VII] Wherein X ₂ is -COOM ', -OH, -SO ₃ M', -CONH ₂ , -S
_{O 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 a hydrogen atom, m ₉ and n ₉ each represent 1 to 10
Represents an integer. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ and
R ₁₈ is a hydrogen atom, a lower alkyl group, an acyl group or R ₁₆ represents a lower alkyl group, and R ₁₉ represents -NR
₂₀ represents R ₂₁ , -OR ₂₂ or -SR ₂₂ , R ₂₀ and R ₂₁ each represent a hydrogen atom or lower alkyl, and R ₂₂ represents R
Represents an atom group necessary for forming a ring by combining with ₁₈ .
R ₂₀ or R ₁₁ may combine with R ₁₈ to form a ring.
M 'represents a hydrogen atom or a cation.

General formula [VIII] 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 alkyl group; x and y each represent 0 or 1; Express. G ′ represents an anion,
z represents 0, 1 or 2.

General formula [IX] In the formula, R ₂₉ and R ₃₀ each represent an atom, an alkyl group, an aryl group or a heterocyclic group, R ₃₁ represents a hydrogen atom or an alkyl group, and R ₃₂ represents a hydrogen atom or a carboxy group.

[Specific Configuration of the Invention] In the present invention, the color developing solution contains at least one compound represented by the general formula [A]. Hereinafter, the compound represented by the general formula [A] is referred to as the compound of the present invention.

In the general formula [A], R ¹ and R ² simultaneously represent an alkyl group or a hydrogen atom which is not a hydrogen atom,
The alkyl groups represented by R ¹ and R ² may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl groups of R ¹ and R ² include those having a substituent, and R ¹ and R ² may combine to form a ring, for example, may form a heterocyclic ring such as piperidine or morpholine. .

Specific examples of the hydroxyamine-based compound represented by the general formula [A] are described in U.S. Pat. Nos. 3,287,125 and 3,293,095.
No. 34, No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention usually contain free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate,
It is used in the form of phosphate, acetate, etc.

The concentration of the compound represented by the general formula [A] of the present invention in the color developer is usually 0.1 g / to 50 g /, preferably 1 g / g.
3030 g /, more preferably 3 g / 〜20 g /.

The compound represented by the general formula [A] of the present invention is used in a conventional color developing solution for a silver halide color photographic light-sensitive material in place of hydroxylamine sulfate which has been widely used as a preservative. However, among the compounds of the present invention, for example, N, N-diethylhydroxylamine is known to be used as a preservative for a black-and-white developing agent in a color developing solution to which a black-and-white developing agent is added. In a so-called external color developing method in which a color photographic light-sensitive material is developed by a reversal method using a color developing solution containing a coupler, there is a technique used together with phenidone. (Tokukosho 45
-22198).

Another example of using the compound of the present invention such as N, N-diethylhydroxylamine as a preservative of a black-and-white developing agent added to a color developing solution is a color developing solution in an internal type color developing solution. A technique for preserving the phenidone derivative added therein (see JP-A-53-32035) and a technique for preserving the phenidone derivative together with hydroquinones (see JP-A-52-153437) Can be.

However, after processing with a color developer containing the compound represented by the general formula [A] as a preservative, the compound has a bleaching ability in the presence of a bleaching accelerator represented by the general formulas [I] to [IX]. The fact that treatment with a processing solution not only provides a significant bleach accelerating effect, but also hardly causes poor recoloring, which has been apt to occur when using a conventional bleaching accelerator, is completely unpredictable. is there.

In the present invention, the "processing solution having a bleaching ability" refers to a processing solution for at least bleaching a light-sensitive material, and specifically refers to a bleach bath or a bleach-fix bath.

In the present invention, the processing solution having the bleaching ability contains at least one compound selected from the compounds represented by the general formulas [I] to [IX].

The compounds represented by the general formulas [I] to [IX] used in the present invention are compounds generally used as a bleaching accelerator, and are hereinafter referred to as bleaching accelerators of the present invention.

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

Illustrative compounds (II-8) H ₂ N-CSNHNHCS-NH ₂ (II-9) H ₂ N-CSNH (CH ₂ ) ₂ NHCS-NH _{2 (III-1) H 2 N} -CH 2 CH 2 -SH (III-4) HOOC-CH 2 CH 2 -SH (VII-3) SCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H) ₂ (VII-17) 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-10, 11, I-13 and I-1 described on pages 51 to 115 of the specification of 263568.
6, I-18, I-20, 21, I-23, I-26, 27, I-30-3
3, I-35, I-38, II-2 to 5, II-7 to 10, II-12,
13, II-15-20, II-22, II-24,25, II-27, II-29
~ 33, II-35,36, II-38-41, II-43, II-45-52, I
I-54,55, II-57, II-59,60, II-62 to 64, II-67 to 7
0, II-73 to 76, II-78,79, II-81 to 84, II-86,87, I
I-90,91, II-93,94, II-96, II-98,99, II-101,10
2, II-104, II-106 to 108, II-110, II-112, II-11
4-119, II-121-124, II-126, II-128-131, II-1
33-135, II-137-144, II-146, II-148, II-150-
153, II-155, II-157, III-4, III-6 to 8, III-
10,11, III-13, III-15, III-17,18, III-20, III
-25, III-27, III-29, III-31, III-35,36, V-
3-6, V-8-14, V-16-20, V-22-25, V-27
~ 29, V-31 ~ 33, V-35 ~ 38, V-40 ~ 42, V-44 ~
46, V-48 to 56, V-58, V-60 to 66, V-68 to 70, V
-72 to 74, V-76 to 79, V-81,82, V-84 to 100, V-
102-108, V-110, V-112,113, V-116-119, V-
121-123, V-126-130, V-132, V-134-138, V
-140 to 144, V-146 to 156, V-158 to 162, V-164 to 1
71, V-173,174, V-177 to 184, VI-4, VI-7, VI
-13, VI-16, VI-19, VI-21, VI-25, VI-27, VI-
Compounds 29, VI-31 to 34 and VI-36 can be used in the same manner.

The bleaching accelerator of the present invention may be present when bleaching a silver image obtained by development, and is preferably added to a bleaching and / or bleach-fixing bath, and is preferably added to a bleaching and / or bleach-fixing bath. Bleaching and / or bleaching by adding to a bath (preprocessing solution) and bringing in with a silver halide color photographic light-sensitive material
Alternatively, it can be contained in a bleach-fix bath. Alternatively, it may be contained in a silver halide color photographic light-sensitive material.

These bleaching accelerators of the present invention may be used alone,
Two or more kinds may be used in combination, and a processing solution 1 having bleaching ability
0.03 to 10 g is preferable, and more preferably, the processing solution 1
It is 0.05 to 2 g per unit.

When the bleaching accelerator of the present invention is added to a bleaching bath, a bleach-fixing bath and / or a bath (pretreatment bath) preceding the bleach-fixing bath, it may be added and dissolved as it is, but water, alkali, organic acid, etc. Is generally added in advance by dissolving in water. If necessary, dissolution and addition using an organic solvent such as methanol, ethanol, or acetone has no effect on the bleaching acceleration effect.

The processing solution having bleaching ability used in the present invention means a bleaching or bleach-fixing solution as described above, and any bleaching agent can be used as a bleaching agent used in these bleaching or bleach-fixing solutions. Red blood salt, iron chloride (UK Patent No. 736,881, described in JP-B-56-44424), persulfuric acid (described in German Patent No. 2,141,199), hydrogen peroxide (JP-B-58-11617, 58) Other than the above, an organic ferric complex salt such as a ferric ethylenediaminetetraacetic acid complex salt is used.

Particularly preferred specific examples are ferric complex salts of organic acids shown below.

(1) diethylenetriaminepentaacetic acid (2) diethylenetriaminepentamethylenephosphonic acid (3) cyclohexanediaminetetraacetic acid (4) ethylenediaminetetraacetic acid (5) methyliminodiacetic acid (6) propyliminodiacetic acid (7) butyliminodiacetic acid (8) cyclohexane Diamine tetramethylene phosphonic acid (9) Triethylene tetramine hexamethylene acetate (10) Triethylene tetramine hexamethylene phosphonic acid (11) Glycol ether diamine tetra methylene phosphonic acid (12) Glycol ether diamine tetra methylene phosphonic acid (13) 1,2-Diaminopropane Tetraacetic acid (14) 1,2-diaminopropanetetramethylenephosphonic acid (15) 1,3-diaminopropan-2-oltetraacetic acid (16) 1,3-diaminopropan-2-oltetramethylenephosphonic acid (17) Ethylenediamine diorthohydroxyphenyl Acetic acid (18) Ethylenediaminediorthohydroxyphenylmethylenephosphonic acid (19) Ethylenediaminetetramethylenephosphonic acid (20) N-hydroxyethyliminodiacetic acid (21) 1,3-Diaminopropanetetraacetic acid (20) 1,3-Diaminopropane Tetramethylenephosphonic acid The ferric complex salt of an organic acid is 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. But preferably potassium, sodium 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 used can be arbitrarily selected, and it is necessary to select the amount according to the silver amount and silver halide composition of the photosensitive material to be processed,
Generally, it has a high oxidizing power and can be used at a lower concentration than other aminopolycarboxylates. For example, it can be used in an amount of 0.01 mol or more per processing solution having a bleaching ability, preferably 0.05 to 0.1.
Used in 6 moles. In the replenisher, it is desirable to use the replenisher concentrated to the full solubility in order to reduce the concentration.

The bleaching solution and the bleach-fixing solution can be used at a pH of 0.2 to 9.5, preferably 4 to 9, more preferably 5.5 to 8.5. The temperature of the treatment is used below 80 ° C, preferably
It is used at 55 ° C. or lower, most preferably at 45 ° C. or lower while suppressing evaporation and the like.

The bleaching solution may contain various additives together with the ferric organic acid complex as a bleaching agent as described above. As an additive, it is particularly desirable to include an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide and the like. Borate, oxalate, acetate, carbonate, phosphate, etc.
pH buffer, solubilizing agent such as triethanolamine, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, alkylamines, polyethylene oxides etc. Those known to be added can be added as appropriate.

In the bleach-fix solution, a bleach-fix solution having a composition in which a small amount of a halogen compound such as potassium bromide is added, or a bleach-fix solution having a composition in which a large amount of a halogen compound such as potassium bromide or ammonium bromide is added, Further, a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can be used.

As the halogen compound, in addition to potassium bromide, hydrogen chloride, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide and the like can also be used.

As the silver halide fixing agent contained in the bleach-fix solution, a compound capable of forming a water-soluble complex salt by reacting with silver halide used in a usual fixing process, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate Representative examples thereof include thiosulfates, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea, thioether, and high concentrations of bromide and iodide. These fixatives are 5g
/, Preferably 50 g / or more, more preferably 70 g / or more in a range that can be dissolved.

As in the case of the bleaching solution, the bleach-fixing solution includes boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide and the like. A pH buffer consisting of various salts can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents, surfactants and deterrents can be added. Preservatives such as hydroxyamine, hydrazine, sulfite, isometric bisulfite, bisulfite adduct of aldehyde and ketone compounds, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid , Organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids or stabilizers such as nitro alcohols and nitrates, solubilizing agents such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, dimethylformamino And dimethyl sulfoxide and the like.

When a fixing solution is used in the present invention, the fixing solution may be, for example, thiosulfuric acid (JP-A-57-185435) as a fixing agent.
Thiocyanate (British Patent No. 565,135)
No., JP-A-54-137143), halides (described in JP-A-52-130639), thioethers (described in Belgian Patent No. 626,970), thioureas (described in British Patent No. 1,189,416) ) Etc. can be used.
In addition to these fixing agents, the fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, as in the bleach-fixing solution. A pH buffer consisting of various salts such as sodium acetate and ammonium hydroxide can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents, surfactants and deterrents can be added. Preservatives such as hydroxyamine, hydrazine, sulfite, isobisulfite, bisulfite adducts of aldehydes and ketone compounds,
Acetylacetone, phosphonocarboxylic acid, polyphosphoric acid,
Organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid,
Organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids or stabilizers such as nitro alcohols and nitrates, solubilizing agents such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, dimethylformamide, dimethyl An organic solvent such as sulfoxide can be appropriately contained.

In the processing of the present invention, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution and a bleach-fixing solution, as well as a stabilizing solution alternative to washing. In this case, for example, an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (JP-A-52-73037, German Patent No. 2,331,2)
No. 20), ion exchange method (JP-A-51-17114)
And the metal substitution method (described in British Patent No. 1,353,805) can be effectively used.

The processing method of the present invention is particularly effective when bleaching or bleach-fixing processing is performed immediately after color development. In such a processing method, the color developing solution is mixed and accumulated in the bleaching or bleach-fixing solution by the photosensitive material by continuous processing. When the mixing ratio of the color developing solution into the bleaching or bleach-fixing solution is 3% or more, especially 5% or more, the bleaching acceleration effect of the bleaching accelerator is reduced and recoloring failure is remarkable. The processing method of the invention is particularly effectively used.

In the present invention, a color developing solution, bleaching and fixing processing may be performed, or bleach-fixing processing after color development may be performed. In addition, JP-A-61
As described in JP-A-75353, a bleaching process may be performed after color development, followed by a bleach-fixing process. In this case, as shown in JP-A-61-75352, the overflow of the bleaching bath may be introduced into the bleach-fixing bath. Also JP
As shown in JP-A-58-105148, bleaching may be performed after pre-fixing, or as shown in JP-A-61-51148, bleach-fixing may be performed after pre-fixing. . In this case, the overflow of the pre-fixing bath may be introduced into the bleach-fixing bath as disclosed in JP-A-61-51143.

Representative specific examples of the processing steps used in the processing method of the present invention are shown below. Among the following processing steps, the steps enclosed by □ are the steps containing the bleaching accelerator of the present invention.

The bleaching acceleration in the above step is a prebath containing a bleaching accelerator.

The compound of the present invention represented by the general formula [A] may be used in combination with other preservatives. Examples of the preservatives that can be used in combination include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like. And bisulfite adducts of aldehydes or ketones such as bisulfite adduct of formaldehyde and bisulfite adduct of glutaraldehyde.

The color developing agent used in the color developing solution of the present invention includes various ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of a salt, for example in the form of the hydrochloride or sulfate, for stability in the free state. It is generally preferred that these compounds are used in a concentration of about 0.1 g to about 50 g per color developing solution 1,
More preferably, a concentration of about 1 g to about 30 g per 1 is used.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, and 5-amino-2.
-Hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful color developers are N, N-dialkyl-p-phenylenediamine type compounds, wherein the alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compounds are N, N-diethyl-p-phenylenediamine hydrochloride, N-methyl-
p-phenylenediamine hydrochloride, N, N-dimethyl-p-
Phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4
-Aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline sulfate, 4-amino-3-methyl-N, N-diethylaniline sulfate, 4-amino-N
-(Methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate;

The color developing agents may be used alone or in combination of two or more kinds, and if necessary, used in combination with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or methol. You may.

Further, instead of using the above color developing agent in the color developing solution, a color developing agent can be added to the light-sensitive material. In this case, the color developing agent used is, for example, a dye precursor. A typical dye precursor is disclosed in
Nos. 58-65429 and 58-24137, and specifically, for example, 2 ', 4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4' -(2,4,6-triisopropyl) benzenesulfonamido-2-methyl-4-N-
(2-methanesulfonamidoethyl) ethylaminodiphenylamine, 2'-methanesulfonamido-4'-
(2,4,6-triisopropyl) benzenesulfonamido-4- (hydroxytrisethoxy) diphenylamine, 4-N- (2-methanesulfonamidoethyl) ethylamino-2-methyl-2 ', 4'-bis ( (2,4,6-triisopropyl) benzenesulfonamidediphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'- (2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 4-methoxy-2'-methanesulfonamide-4 '
-(2,4,6-triisopropyl) benzenesulfonamidodiphenylamine, 4-dihexylamino-4'-
(2,4,6-triisopropylbenzenesulfonamide)
Diphenylamine, 4-n-hexyloxy-3'-methyl-4 '-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine, 4-N, N-diethylamino-4'-(2,4,6- Triisopropylbenzenesulfonamido) diphenylamine, 4-N, N-dimethylamine-2-phenylsulfonyl-4 '-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine and the like.

The amount of the dye precursor added to the photosensitive material is preferably 0.5 to 22 mg, more preferably ^{4 to 12} mg, per 100 cm ² of the photosensitive material.

The color developing solution may contain the following developing solution components in addition to the above components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium carbonate, potassium carbonate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination And can be used. Further, various kinds of disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like are used for the purpose of preparation or for the purpose of increasing ionic strength. be able to.

If necessary, inorganic and organic antifoggants can be added.

Further, a development accelerator can be used if necessary. U.S. Pat.Nos. 2,648,604 and
No. 3,671,247, various pyridinium compounds represented by JP-B-44-9503 and other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.Nos. 2,533,990, 2,531,8
No. 32, 2,950,970, 2,577,127, and polyethylene glycol and derivatives thereof described in JP-B-44-9504, nonionic compounds such as polythioethers, organic solvents described in JP-B-44-9509 and Organic amine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like are included. Also, benzyl alcohol, phenethyl alcohol and others described in U.S. Pat.No. 2,304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone,
Thioethers, pyridine, ammonia, hydrazine,
Aminos and the like can be mentioned.

Further, the color developing solution of the present invention may contain, as necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, JP-B-44-9509. Can be used as an organic solvent for increasing the solubility of the developing agent.

Examples of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; oxycarboxylic acids such as citric acid and gluconic acid; organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid; Methylene phosphonic acid)
And polyhydroxy compounds such as 1,2-dihydroxybenzene-3,5-disulfonic acid.

Other compounds that can be added to the color developing solution of the present invention include fluorescent whitening agents, especially triazylstilbene-based fluorescent whitening agents, and alkanolamines such as polyethyleneimine.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetra Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g /. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (a so-called DIR coupler), a development inhibitor releasing compound, or the like can be added.

Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

Each component of the color developing solution can be prepared by sequentially adding to a certain amount of water and stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state is added to water and stirred to prepare a color developer of the present invention. Obtainable.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but is preferably from pH 9.5 to 13.0, more preferably from pH 9.8 to 13.0, from the viewpoint of rapid processing.

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the faster the processing can be performed in a shorter time, which is preferable. However, it is preferable that the temperature is not so high from the viewpoint of image storage stability.

In the present invention, washing with water or an alternative stabilizing treatment with washing instead of water is performed.

Hereinafter, the washing stabilizing solution applicable to the present invention will be described.

The pH of the washing alternative stabilizer applicable to the present invention is preferably in the range of 5.5 to 10.0, and more preferably pH 6.3 to 9.5.
And particularly preferably in the range of pH 7.0 to 9.0. As the pH adjusting agent that can be contained in the washing-substitute stabilizing solution applicable to the present invention, any commonly known alkali agent or acid agent can be used.

The treatment temperature of the stabilization treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ℃ to 45 ℃ is good. The processing time is also preferably shorter from the viewpoint of rapid processing, but usually 20 seconds to 10 minutes,
The time is most preferably 1 minute to 3 minutes. In the case of the multiple tank stabilization treatment, it is preferable that the treatment is performed in a shorter time in the former tank and the treatment time is longer in the latter tank. In particular, it is desirable to sequentially perform the treatment with a treatment time that is 20% to 50% longer than that of the preceding tank. No water washing treatment is required after the stabilization treatment applicable to the present invention, but rinsing by small amount of water washing and surface washing in an extremely short time can be arbitrarily performed as necessary.

In the case of using a multi-tank countercurrent method, it is preferable to supply a post-bath bath and overflow from a pre-bath, when a stabilizing treatment step applicable to the present invention is supplied in a stabilizing treatment step using a multi-tank countercurrent method. Of course, it can also be processed in a single tank. As a method of adding the above compound, the compound and other additives are added to a stabilization tank as a concentrated solution, or the above-mentioned compound and other additives are added to a stabilization tank to be replaced with a water washing alternative stabilizing solution. Although there are various methods such as a method of supplying the liquid, the liquid may be added by any method.

As described above, in the present invention, the treatment with the washing substitute stabilizer refers to a treatment for a stabilization treatment that does not substantially perform the washing treatment, and the treatment liquid used for the stabilization treatment is referred to as a washing substitute stabilizer, The tank is called a stabilizing bath or stabilizing tank.

The stabilization tank in the stabilization treatment applicable to the present invention is 1 to
When the number of tanks is five, the effect of the present invention is large, particularly preferably one to three tanks, and preferably at most nine tanks or less.

Silver halide emulsions usable in the light-sensitive material applicable to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide and silver chloroiodobromide. Any of these silver halides may be used. The processing method of the present invention is a method for processing a silver halide color photographic light-sensitive material containing silver halide grains containing at least 0.5 mol% of silver iodide, and 2 mol% to 20 mol% of silver iodide. Particularly suitable for processing silver halide color photographic light-sensitive materials containing silver halide grains containing.

The silver halide emulsion layer according to the present invention can contain a coupler, that is, a compound capable of forming a dye by reacting with an oxidized form of a color developing agent.

As the coupler usable in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without any particular limitation. These couplers may be so-called two-equivalent type or four-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler in combination with these couplers.

Useful cyan couplers used in the present invention include:
For example, phenol-based and naphthol-based couplers can be used. Specific examples of cyan couplers include U.S. Pat.Nos. 2,369,929, 2,434,272, 2,474,293 and 2,5.
21,908, 2,895,826, 3,034,892, 3,311,47
No. 6, No. 3,458,315, No. 3,476,563, No. 3,583,971,
3,591,383, 3,767,411, 3,772,002, 3,9
33,494, 4,004,929, West German Patent Application (OLS) 2,414,
830, 2,454,329, JP-A-48-59838, 51-260
No. 34, No. 48-5055, No. 51-146827, No. 52-69624
No. 52-90932, No. 58-95346, JP-B-49-11572
And the like.

As the magenta coupler, compounds such as pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds are used. As the pyrazolone-based magenta coupler, U.S. Pat.
3,062,653, 3,127,269, 3,311,476, 3,41
9,391, 3,519,429, 3,558,318, 3,684,514
No. 3,888,680, JP-A-49-29639, JP-A-49-111631
No. 49-129538, No. 50-13041, JP-B 53-47167
Nos. 54-10491, 55-30615, the compounds described in the pyrazolotriazole magenta coupler, U.S. Pat.No.1,247,493, and the couplers described in Belgian Patent 792,525 include, As the colored magenta coupler, a compound having an arylazo substituent at the coupling position of a colorless magenta coupler is generally used.For example, U.S. Patent Nos. 2,801,171 and 2,983,608
Nos. 3,005,712 and 3,684,514, UK Patent 937,621
And JP-A-49-123625 and JP-A-49-31448.

Further, a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391 in which a dye flows out into a processing solution by reaction with an oxidized form of a developing agent can also be used.

As the yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetoanilide type yellow coupler and a pivaloylacetoanilide type yellow coupler which are generally widely used can be used. Further, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction are also advantageously used. Examples of these are U.S. Pat.Nos. 2,875,057, 3,265,506,
664,841, 3,408,194, 3,277,155, 3,447,9
No. 28, 3,415,652, JP-B-49-13576, JP-A-48-48
29432, 48-68834, 49-10736, 49-12233
No. 5, No. 50-28834 and No. 50-132926 are described together with the synthesis method.

The amount of the diffusion-resistant coupler used in the present invention is generally 0.05 to 0.05 mol per mol of silver in the photosensitive silver halide emulsion layer.
~ 2.0 mol.

In the present invention, a DIR compound is preferably used in addition to the above-mentioned diffusion-resistant coupler.

Further, in addition to the DIR compound, compounds that release a development inhibitor upon development are also included in the present invention.
3,297,445, 3,379,529, West German Patent Application (OLS) 2,4
No. 17,914, JP-A-52-15271, JP-A-53-9116, and JP-A-59-1
Nos. 23838 and 59-127038.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers described in Research Disclosure Magazine No. 17643,
Color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
An arbitrary one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support of the silver halide color photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support having a reflective layer, or a reflective plate, such as a glass plate, Examples include a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and may be other ordinary transparent supports. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,79
A simultaneous coating method of two or more layers according to the method described in JP-A Nos. 1 and 2,941,898 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer may be appropriately used as constituent layers. It can be used in combination. In these constituent layers, a hydrophilic colloid which can be used in the above-mentioned emulsion layer can be similarly used as a binder, and various layers which can be contained in the above-mentioned emulsion layer can be contained in the layer. Photographic additives.

In the method for processing a silver halide color photographic light-sensitive material of the present invention,
Color papers, color negative films, color positive films, color reversal films for slides, color reversal films for movies, color reversal films for TV, as long as the photosensitive material contains a coupler in the photosensitive material and is processed by the so-called internal development method And any silver halide color photographic light-sensitive material such as reversal color paper.

[Specific Effects of the Invention] As described above, according to the present invention, an excellent silver halide color photographic light-sensitive material having a rapid silver bleaching ability and having extremely little deterioration in the recoloring property of a cyan dye. A processing method can be provided.

[Specific Examples of the Invention] Hereinafter, the present invention will be described specifically with reference to Examples, but embodiments of the present invention are not limited thereto.

Example 1 The antihalation layer and the red-sensitive silver halide were applied from the support side with various auxiliary layers in accordance with the layer structure employed for high-sensitivity silver halide color photographic materials in the art. An emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer were provided, and a monodispersed high-sensitivity silver halide emulsion layer was disposed on the outermost side of the blue-sensitive silver halide emulsion layer. The coated silver amount was approximately 13 mg / dm ² for the blue-sensitive silver halide emulsion layer and approximately 18 mg for the green-sensitive silver halide emulsion layer.
/ dm ² , and the concentration of the red-sensitive silver halide emulsion layer was adjusted to approximately 13 mg / dm ² .

Layer 1: A dispersion of 0.8 g of black colloidal silver exhibiting high absorbency for light in the wavelength range of 400 to 700 nm by reducing with hydroquinone using silver nitrate as a reducing agent was prepared with 3 g of gelatin to form an antihalation layer.

Layer 2: Intermediate layer made of gelatin (dry film thickness: 0.8 μm) Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (Ag I; 6 mol%), 1.9 g of gelatin and 0.96 g of 1- Hydroxy-4- (β-methoxyethylaminocarbonylmethoxy) -N- [δ- (2,4-di-t-amylphenoxy) butyl] -2-naphthamide (hereinafter referred to as cyan coupler (C-1)) 0.028 g of 1-hydroxy-4
-[4- (1-hydroxy-8-acetamido-3,6-
Disulfo-2-naphthylazo) phenoxy] -N- [δ
-(2,4-di-t-amylphenoxy) butyl] -2-
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter, referred to as TCP) in which naphthamide disodium (hereinafter, referred to as colored cyan coupler (CC-1)) is dissolved. .

Layer 4: 1.1 g of high-sensitivity red-sensitive silver iodobromide emulsion (Ag I; 8 mol%) 1.2 g of gelatin, 0.41 g of cyan coupler (C-1), 0.026 g of colored cyan coupler (CC-1) A) a high-sensitivity red-sensitive silver halide emulsion layer containing 0.15 g of TCP dissolved therein.

Layer 5: 0.04 g in which 0.08 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as a stain inhibitor (HQ-1)) was dissolved.
An intermediate layer containing g of dibutyl phthalate (hereinafter referred to as DBP) and 1.2 g of gelatin.

Layer 6: 1.6 g of low-sensitivity green photosensitive silver iodobromide emulsion (Ag I; 15 mol%), 1.7 g of gelatin and 0.30 g of 1-
(2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacetamide) benzeneamide] -5-pyrazolone (hereinafter referred to as magenta coupler (M-
1)), 0.20 g of 4,4-methylenebis-11- (2,4,
6-trichlorophenyl) -3- [3- (2,4-di-t-
Aminophenoxyacetamide) benzeneamide] -5
-Pyrazolone (hereinafter referred to as magenta coupler (M-2)), 0.066 g of 1- (2,4,6-trichlorophenyl)-
Dissolves three types of couplers, 4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) Low-sensitivity green-sensitive silver halide emulsion layer containing 0.3 g of TCP.

Layer 7: High sensitivity green photosensitive silver iodobromide emulsion (Ag I; 11 mol%), 1.9 g of gelatin, 0.093 g of magenta coupler (M-1), 0.094 g of magenta coupler (M-2), 0 .
049 g of colored magenta coupler (CM-1) was dissolved
High-sensitivity green-sensitive silver halide emulsion layer containing 1.2 g of TCP.

Layer 8: 0.2 g of yellow colloidal silver, 0.2 g of stain inhibitor (HQ-
Yellow filter layer containing 0.11 g of DBP dissolved in 1) and 2.1 g of gelatin.

Layer 9: 0.95 g of a low-sensitivity blue-sensitive silver iodobromide emulsion (Ag I; 6 mol%), 1.9 g of gelatin and 1.84 g of α-
[4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-2
-Sensitive blue light containing 0.93 g of DBP in which -chloro-5- [γ- (2,4-di-t-aminophenoxy) butanamide] acetanilide (hereinafter referred to as yellow coupler (Y-1)) is dissolved. Silver halide emulsion layer.

Layer 10: 1.2 g of a high-sensitivity monodisperse blue-sensitive silver iodobromide emulsion (Ag
I; 7 mol%), 2.0 g of gelatin and 0.23 g of DBP in which 0.46 g of yellow coupler (Y-1) is dissolved, a high-sensitivity blue-sensitive silver halide emulsion layer.

Layer 11: Second protective layer made of gelatin.

Layer 12: First protective layer containing 2.3 g of gelatin.

The color temperature of the sample obtained above was adjusted to 4800 ° K with a filter using a tungsten light source, and a 20CMS wedge exposure was given.

 The exposed photosensitive material was subjected to the following processing.

Processing steps are color development 3 minutes 15 seconds, bleaching 2 minutes 30 seconds, fixing 3
Minute 15 seconds, first stable 2 minutes, second stable 30 seconds.

Each treatment was performed at 37.8 ° C., and each treatment liquid used was a treatment liquid prepared according to the following formulation.

The amount of silver remaining in the maximum dye density part of the sample after processing was determined by fluorescence X
The bleach accelerating effect was evaluated by the linear method. Furthermore, the maximum transmission density of the cyan dye was measured with an optical densitometer PDA-65 (manufactured by Konishi Roku Kogyo Co., Ltd.), followed by treatment in an oxidation bath containing 3% red blood salt at 35 ° C. for 3 minutes to remove the cyan dye. The maximum transmission density of the cyan dye of the sample which had been sufficiently recolored was measured again, and the reproducibility was evaluated by obtaining the difference ΔD _R from the density of the cyan dye before recoloring.

 The results are shown in Table 1.

As is evident from Table 1, when a hydroxylamine sulfate other than the present invention is used, even if the bleaching accelerator of the present invention is used, the bleaching is not sufficiently bleached within the bleaching time of the present example, and Although the amount of silver remaining is large, it can be seen that a good bleach accelerating effect can be obtained by using the hydroxylamines of the present invention.

When a hydroxylamine sulfate other than the present invention is used, by using the bleaching accelerator of the present invention,
Although poor recoloring occurs, it can be seen that poor recoloring hardly occurs by using the hydroxylamines of the present invention.

When each of the hydroxylamines was used in a color developing solution, (I-6) was used as a bleaching accelerator,
(I-13), (II-23), (II-29), (II-40),
(II-45), (III-3), (IV-1), (V-17),
The treatment using each of (VI-20), (VII-17) and (VIII-2) was further performed, and almost the same results were obtained as when the bleaching accelerators shown in Table 1 were used. .

Example 2 A bleach-fixing process was performed for 3 minutes and 15 seconds using the light-sensitive material used in Example 1 and a bleach-fix solution having the following composition in place of the bleach-fixing process of Example 1.

The hydroxylamines in the color developing solution were those described in Table 2 in the amounts shown in Table 2.

In the same manner as in Example 1, the samples after the treatment were evaluated for the bleach accelerating effect and the color reproducibility.

 The results are shown in Table 2.

As is clear from Table 2, when a hydroxylamine sulfate other than the present invention was used in a system using a bleach-fix bath, the bleach-fixing time of the present example was obtained even when the bleach accelerator of the present invention was used. Although the amount of silver remaining in the light-sensitive material without being bleach-fixed sufficiently is large, it can be seen that a good bleach accelerating effect can be obtained by using the hydroxylamines of the present invention.

When a hydroxylamine sulfate other than the present invention is used, by using the bleaching accelerator of the present invention,
Although poor recoloring occurs, it can be seen that poor recoloring hardly occurs by using the hydroxylamines of the present invention.

In the case where each of the hydroxylamines was used in a color developing solution, (I-6)
(I-13), (II-23), (II-29), (II-40),
(II-45), (III-3), (IV-1), (V-17),
Further treatments using (VI-20), (VII-17) and (VII-2) yielded almost the same results as when the bleaching accelerators shown in Table 2 were used.

Example 3 After the bleaching process was performed for 40 seconds using the light-sensitive material used in Example 1 and a bleaching solution and a bleach-fixing solution having the following composition in place of the bleaching and fixing processes in Example 1, And a bleach-fixing process was performed for 3 minutes and 15 seconds.

The hydroxylamines in the color developing solution were those described in Table 3 in the amounts shown in Table 3.

The samples after the treatment were evaluated for the bleach accelerating effect and the color reproducibility in the same manner as in Example 1.

 The results are shown in Table 3.

As is clear from Table 3, when a hydroxylamine sulfate other than the present invention was used, the bleach accelerating effect was small and the color reproducibility was poor, but the mixing amount of the color developing solution in the bleaching solution was 3% or more. In particular, at 5% or more, the bleach accelerating effect is remarkably reduced, and the reproducibility is greatly deteriorated. However, by using the hydroxylamines of the present invention, the mixing ratio of the color developing solution in the bleaching solution increases. It can be seen that both the bleach accelerating effect and the color reversibility are good. Further, as the hydroxylamines, the exemplified compounds (A-3) and (A-
8), (A-9), (A-12), (A-22) and (A-
24) was used, but almost the same good results were obtained.

Claims (1)

(57) [Claims] 1. A silver halide having at least one layer on a support
Imagewise processing of silver halide color photographic materials having an emulsion layer
Has at least a color developing solution and bleaching ability
Silver halide color photographic light-sensitive material processed with a processing solution
In the method for treating a silver halide emulsion, iodide is added to the silver halide emulsion layer.
Contains silver halide grains with a silver content of 0.5 mol% or more
Silver halide color photographic light-sensitive material is used as a color developer.
At least one of the compounds represented by the following general formula [A]
As a processing solution having bleaching ability, the following general formula
Selected from the compounds represented by [I] to [IX], respectively.
Contains at least one compound and has the bleaching ability
The color developing solution is mixed into the processing solution at a rate of 5% or more.
Of silver halide color photographic light-sensitive material characterized by the following
Method. General formula [A](Where R¹And R^TwoRepresents an alkyl group or a hydrogen atom, respectively.
You. Where R¹And R^TwoThat both are hydrogen atoms at the same time
Absent. Also R¹And R^TwoMay form a ring. ) General formula [I][In the formula, Q represents a nitrogen-containing heterocyclic ring (a 5- to 6-membered unsaturated ring is condensed.
List of atoms necessary to form
Then R₁Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Cycloalkyl group, aryl group, heterocyclic group (5 to 6 members
(Including those fused with unsaturated rings) or amino group
Represents General formula [II](Where R_TwoAnd R_ThreeRepresents a hydrogen atom and a carbon atom
6, alkyl group, hydroxy group, carboxy group, amino
Groups, acyl groups having 1 to 3 carbon atoms, aryl groups or
Represents a alkenyl group. A is Or n₁Divalent heterocyclic residue (where a 5- or 6-membered unsaturated ring is fused
X is = S, = O or = N
R ″, where R and R ′ are each R_TwoAnd R_ThreeSame as
X'H 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, orM represents a divalent metal atom, R ″ represents a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group,
Reel group, heterocyclic residue (5 to 6-membered unsaturated ring
Represents an amino group, n₁~ N₆And
M₁~ M_FiveEach represents an alkylene group of 1 to 6, Y is
-N = or -CH =, R_FourAnd R_FiveIs R_TwoYou
And R_ThreeIs synonymous with Where R_FourAnd R_FiveMay each represent -B-SZ,
Also R_TwoAnd R_Three, R and R ', R_FourAnd R_FiveAre bonded to each other to form a ring
It may be formed. The compound represented by the formula is an enol compound and its compound
Including salt. General formula [III](Where R₆And R₇Represents a hydrogen atom and a carbon atom
6, alkyl group, hydroxy group, carboxy group, amino
Group, an alkyl group having 1 to 3 carbon atoms, an aryl group or
Alkenyl group or -B₁-S-Z₁Represents Where R₆And R₇
May combine to form a ring. Y₁Is -N = or -CH
= And B₁Represents an alkylene group having 1 to 6 carbon atoms.
Then Z₁Is hydrogen atom, alkali metal atom, ammonium
Group, amino group, nitrogen-containing heterocyclic residue orRepresents n₇Represents an integer of 1 to 6. General formula [IV](Where R₈And R₉Are each And R_TenIs an alkyl group or-(CH_Two) N₈SO_Three The table
You. (However, R_TenIs-(CH_Two) N₈SO_Three When l is 0
And represents 1 when it is an alkyl group. ) G Represents an anion
Represent. n₈Represents an integer of 1 to 6. General formula [V](Where Q₁Is a nitrogen-containing heterocyclic residue (5- to 6-membered unsaturated ring)
Or those containing condensed saturated rings)
Represents the group of atoms required for₁₁Is hydrogen atom, alkali metal
Atom,Or represents an alkyl group. Where Q 'is Q₁Synonymous with
You. General formula [VI](Where D₁, D_Two, D_ThreeAnd D_FourEach is just a bond, charcoal
Represents an alkylene group or a vinylene group having 1 to 8 elementary atoms.
Then q₁, Q_Two, Q_ThreeAnd q_FourRepresents 0, 1, or 2, respectively.
You. The ring formed together with the sulfur atom is further saturated with 5-6.
It may be bonded to a sum or unsaturated ring. General formula [VII](Where X_TwoIs -COOM ', -OH, -SO_ThreeM ', -CONH_Two, -S
O_TwoNH_Two, -SH, -CN, -CO_TwoR₁₆, -SO_TwoR₁₆, -OR₁₆, -N
R₁₆R₁₇, −SR₁₆, -SO_ThreeR₁₆, -NHCOR₁₆, NHSO_TwoR₁₆, -O
COR₁₆Or -SO_TwoR₁₆And Y_TwoIsOr a hydrogen atom, m₉And n₉Is 1 to 10
Represents an integer. R₁₁, R₁₂, R₁₃, R₁₄, R_Fifteen, R₁₇And R₁₈
Represents a hydrogen atom, a lower alkyl group, an acyl group orAnd R₁₆Represents a lower alkyl group; R₁₉Is -NR₂₀R
_{twenty one}, -OR_{twenty two}Or -SR_{twenty two}And R₂₀And R_{twenty one}Each
Represents a hydrogen atom or a lower alkyl group;_{twenty two}Is R₁₈Conclude with
Represents an atom group necessary for forming a ring together. R₂₀Also
Is R₁₁Is R₁₈And may form a ring. M 'is hydrogen
Represents an atom or a cation. General formula [VIII][Wherein, Ar is a divalent aryl group or an aryl group and oxygen
2 in combination with an atom and / or an alkylene group
Represents a valent organic group, B_TwoAnd B_ThreeIs lower-grade
R_{twenty three}, R_{twenty four}, R_{twenty five}, And R₂₆Is low
Represents an alkyl group, and x and y are each 0 or 1
Represent. G ′ represents an anion, and z represents 0, 1 or 2.
You. General formula [IX](Where R₂₉And R₃₀Are hydrogen and alkyl
Group, an aryl group or a heterocyclic group, R₃₁Is hydrogen field
Represents a child or an alkyl group. ]