JP3066778B2 - Color developer for color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution and a processing method for a color photographic light-sensitive material capable of processing to a stable photographic performance in processing a high silver chloride color photographic light-sensitive material.

[0002]

2. Description of the Related Art Recently, the processing of color photographic light-sensitive materials has been greatly accelerated, and the rapid processing of silver chloride-based color paper called Process RA-4 proposed by Eastman Kodak Co., Ltd. It can be processed in 3 minutes.

A color paper using a silver halide emulsion mainly containing silver chloride is more suitable for rapid processing than a conventional color paper using a silver chlorobromide emulsion. For example, W
O-87-04534 discloses a treatment solution that does not contain sulfite ions or benzyl alcohol and uses a hydroxylamine derivative. JP-A-63-106655 discloses a method of processing a color photographic light-sensitive material mainly containing silver chloride with a developing solution containing a hydroxylamine derivative and a chloride having a certain concentration or more.

[0004] However, such a color developing solution containing no sulfite ion has a disadvantage that processing fluctuations are apt to occur due to deterioration of the color developing solution. In addition, the print quality is softened, the color balance fluctuates,
It is difficult to obtain stable quality.

[0005] On the other hand, with the expansion of minilabs in recent years, more and more inexperienced people who do not have sufficient technical skills handle color photographic light-sensitive materials, and there is a great demand for stabilization of processing. is there.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a processing solution and a processing method capable of obtaining excellent quality by stable processing, including running, in the processing of color photographic light-sensitive materials. Is to do.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide a paraphenylene
Amine color developing agent and represented by the following general formula [1]
Contains compounds and sulfite is 3.0 liters per liter
Color development not containing benzyl alcohol at × 10 ^-3 mol or less
Depending on the developer, halogen containing more than 80 mol% of silver chloride
A silver halide color photographic light-sensitive material having silver halide grains,
At a processing temperature of 35 ° C. or more, the replenishment amount of the color developing solution
As it follows down halide color photographic light-sensitive material 1 m ² per 150ml
Silver halide color photographic exposure characterized by processing
Achieved by the material processing method .

[0008]

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[In the formula, Z ₁ represents an atomic group necessary for forming a benzene ring or a nitrogen-containing 6-membered heterocyclic ring, and Z ₂ represents —NH
-Represents a group of atoms necessary to form a pyrazole ring, an imiazole ring or a triazole ring. The ring formed by Z ₁ and Z ₂ includes those having a substituent. The developer contains 3.0 × 10 ^-2 mol / l as chloride.
Containing, hydroxylamine derivatives, hydrazines, hydrazides, α-hydroxyketones,
It is desirable to contain at least one compound selected from α-aminoketones, monoamines, and diamines.

[0010]

Hereinafter, the present invention will be described specifically.

Representative specific examples of the compound represented by the general formula [1] in the present invention are shown below. However, it is not limited to these.

[0013]

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[0014]

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The methods for synthesizing these compounds are well known and can be easily synthesized by those skilled in the art. For the synthesis of these compounds, for example, "New Experimental Chemistry Lecture 14"
(Maruzen) and the like.

When the compound represented by the general formula [1] of the present invention is used by being contained in a developing solution, it varies depending on the kind of the compound, but generally, it is 0.1 to 1 liter per developing solution.
The amount may be from 01 mg to 50 g, and particularly preferably from 0.05 mg to 10 g. The compound of the present invention may be added to an emulsion layer, an intermediate layer and a protective layer of a silver halide color photographic light-sensitive material. In this case, the compound is used in an amount of 0.1 mg to 10 g, preferably 0.2 mg to 2 g per 1 g of silver. You. As described above, the compound of the present invention can be added to either a developing solution or a light-sensitive material, but it is preferable to add the compound to the developing solution in order to use the effect more effectively.

In the present invention, the replenisher for color development contains
A requirement is that sulfurous acid (salt) is not substantially contained.
Here, "substantially not contained" means that the content is not more than 3.0 × 10 ^-3 mol / l, and when it is 0, the effect of the present invention is remarkable. That is, when processing a photosensitive material mainly containing silver chloride, it is preferable that the sulfurous acid concentration is substantially 0 from the viewpoint of developability. However, a small amount of sulfuric acid is added in order to prevent oxidation of the color developing agent for kitting. As a color developer
It may be 3.0 × 10 ⁻³ mol / l or less.

As the paraphenylenediamine-based color developing agent used in the present invention, known compounds are used. Particularly, the color developing agent preferably used in the present invention is described in Japanese Patent Application No. 2-203169, pp. 26-31. (C-1) to (C-16) described below, and the following compound (C-1)
7), (C-18), (C-19) and the like. Among them, (C-1) is a color developing agent which remarkably exerts the effects of the present invention.

[0019]

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The color developing agent is preferably a hydrochloride,
It is used in the form of sulfate, nitrate and p-toluenesulfonate.

The amount of the color developing agent used in the present invention is
The amount is 2.0 × 10 ^-2 mol or more, preferably 2.0 × 10 ^{-2 to} 1.0 × 10 ^-1 mol, per liter of the color developing replenisher.

If the amount of the color developing agent is less than 2.0 × 10 ^-2 mol, it is difficult to achieve rapid and low replenishment with the same chemical.

As the chloride used in the present invention, specifically, potassium chloride, sodium chloride, lithium chloride,
Examples thereof include ammonium chloride and hydrogen chloride, and any other materials that release chloride ions can be used. In the present invention, among these, potassium chloride or sodium chloride is preferably used from the viewpoint of good development characteristics, solubility and handleability, and 3 × 10 ⁻² mol / l or more as chloride in a color developing solution. When it is contained, it has an effect of improving yellow stain in addition to the effect of the present invention, and is therefore mentioned as one of more preferred embodiments of the present invention.

In order to prevent air oxidation of the color developing agent in the color developing solution of the present invention, JP-A-63-146043 is used in place of hydroxylamine conventionally used as a preservative.
No. 63-146042, No. 63-146041, No. 63-146040, No.
63-135938, hydroxylamine derivatives described in 63-118748 and hydroxamic acids described in JP-A-64-62639,
Hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused rings Formula amines and the like are preferably used as the organic preservative.

In particular, hydroxylamine derivatives, hydrazines, hydrazides, α-hydroxyketones, α-hydroxyketones,
When at least one compound selected from aminoketones, monoamines and diamines is contained, it is preferable in terms of developability, and the crystal precipitation on the liquid surface of the color developer tank is also good, and another effect is exhibited. Therefore, it is mentioned as one of more preferred embodiments of the present invention.

The hydroxylamine derivative in the present invention is a compound represented by the following general formula [2].

[0027]

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The detailed description of the general formula [2] is disclosed in Japanese Patent Application No. 2-1788.
This is synonymous with the description of general formula [A] described in No. 33, page 50, page 54, page 55.

Specific examples of the compound represented by the general formula [2] will be given.

2-1 to 15 are Japanese Patent Application No. 2-178833, pages 51 to 53.
Same as pages A-1 to A-15.

[0031]

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2-26 to 49 are Japanese Patent Application No. 2-178833, pages 51 to 53.
Same as pages A-16 to 39.

The hydrazines and hydrazides in the present invention are compounds represented by the following general formula [3].

[0034]

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In the formula, R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a sulfopropyl group, a carboxybutyl group). Group, hydroxyethyl group, etc.), aryl group (preferably having 6 to 20 carbon atoms, such as phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group) or heterocyclic group (preferably Has 1 to 20 carbon atoms, for example, pyridine-4
-Yl group).

R ³⁴ is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a sulfopropyl group, a carboxybutyl group, a hydroxyethyl group, a cyclohexyl group) Group, benzyl group, etc.), aryl group (preferably having 6 to 20 carbon atoms, such as phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group), heterocyclic group (preferably C 1-2
0, for example, a pyridin-4-yl group, etc., an alkoxy group (preferably having 1 to 20 carbon atoms, for example, a methoxy group, an ethoxy group, a methoxyethoxy group, a benzyloxy group, a cyclohexyloxy group, etc.), an aryloxy group (preferably a carbon Formulas 6 to 20, for example, phenoxy group, p-methoxyphenoxy group and the like, carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl group, N, N-diethylcarbamoyl group, hydrazinocarbonyl group) and amino group ( It preferably has 0 to 20 carbon atoms, for example, an amino group, an N-phenylamino group, a hydrazino group and the like.

X ¹ represents a divalent group selected from —CO—, —SO ₂ — and —C (NH) —. n is 0 or 1. Where n =
When 0, R ³⁴ represents a group selected from substituted or unsubstituted alkyl group, aryl group and heterocyclic group. R ³³ and R ³⁴ may form a heterocycle together.

In the general formula [3], R ³¹ , R ³² and R ³³ are preferably a hydrogen atom or an alkyl group.
Most preferably, ³¹ and R ³² are hydrogen atoms.

In the general formula [3], R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group or an amino group. X ¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

Specific examples of the compound represented by the general formula [3] are shown below, but the present invention is not limited thereto.

[0041]

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Other specific examples are described in Japanese Patent Application No. 61-17075.
Compound examples (1-1) to 11 to 16 on page 6
(1-32) and the like.

The compound of the above general formula [2] is disclosed in Japanese Patent Application No. 61-170.
It can be obtained based on the method described in No. 756.

The α-hydroxyketones and α-aminoketones in the present invention are compounds represented by the following general formula [4].

[0045]

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In the formula, R ⁴¹ is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a hydroxymethyl group, a methoxyethyl group, a cyclohexyl group, etc.), an aryl group (Preferably having 6 to 20 carbon atoms, such as a phenyl group and a 2-hydroxyphenyl group), an alkoxy group (preferably having 1 to 20 carbon atoms,
For example, a methoxy group, an ethoxy group, a methoxyethoxy group, etc., an aryloxy group (preferably having 6 to 20 carbon atoms, such as phenoxy group, 4-methoxyphenoxy group, etc.), or an amino group (preferably having 0 to 20 carbon atoms, such as amino Group, N, N-diethylamino group, N-phenylamino group, etc.)
Represents

[0047] R ⁴² is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, such as methyl group, ethyl group, hydroxymethyl, methyl group) or an aryl group (preferably having 6 to 20 carbon atoms, e.g. Phenyl group,
A 2-hydroxyphenyl group).

R ⁴¹ and R ⁴² may together form a carbocyclic or heterocyclic ring.

X ² represents a hydroxyl group or a substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, for example, an amino group, an N, N-diethylamino group, a morpholino group and the like).

In the general formula [4], R ⁴¹ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or an alkoxy group, and R ⁴² is a hydrogen atom or a substituted or unsubstituted alkyl group. Certain cases are preferred.

Specific examples of the compound represented by the general formula [4] are shown below, but the present invention is not limited thereto.

[0052]

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Other specific examples are described in Japanese Patent Application No. 61-18432.
Examples of the compounds (1) to (18) described on page 15 to 18 in the specification of JP-A No. 8 can be mentioned.

The compound of the above general formula [4] is disclosed in Japanese Patent Application No. 61-184.
It can be obtained based on the method described in No. 328.

The amount of the compounds represented by the general formulas [2] to [4] added to the color developing solution is preferably 0.01 g to 100 g, more preferably 0.1 g to 2 g per liter of the color developing solution.
It is 0g.

Next, the monoamines used in the present invention are compounds represented by the following general formula [5].

[0057]

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In the formula, R ⁵¹ and R ⁵² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, and R ⁵³ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group. Represents a group or a heterocyclic group. Where R ⁵¹ and R ⁵² , R ⁵¹ and R ⁵³ or R ⁵² and R
⁵³ may be linked to form a nitrogen-containing heterocyclic ring.

The alkyl groups represented by R ⁵¹ , R ⁵² and R ⁵³ are preferably those having 1 to 12 carbon atoms, and may be linear, branched or cyclic (specifically, methyl, ethyl, n -
Propyl group, iso-propyl group, n-butyl group, t-butyl group, t-amyl group, n-hexyl group, cyclohexyl group, etc.); May be branched or cyclic (specifically, allyl group, isopropenyl group, cyclohexenyl group, etc.); and the aryl group is preferably one having 6 to 12 carbon atoms (specifically, phenyl group, tolyl group, An aralkyl group preferably has 7 to 12 carbon atoms (specifically, a benzyl group, a phenethyl group, etc.); and a heterocyclic group includes a nitrogen atom, an oxygen atom and / or a sulfur atom as a hetero atom. Those containing 1 to 12 carbon atoms are preferable (specifically, imidazolyl group, pyrazolyl group, triazolyl group, pyridyl group and the like).

When R ⁵¹ , R ⁵² and R ⁵³ are other than a hydrogen atom, they may have a substituent. Specific examples of the substituent include a halogen atom (such as a fluorine atom, a chlorine atom, and a bromine atom). Alkyl group (methyl group, ethyl group, butyl group,
t-butyl group, methoxyethyl group, carboxymethyl group,
Hydroxyethyl group, etc.) aryl group (phenyl group, tolyl group, naphthyl group, etc.), alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), aryloxy group (phenoxy group, p-nitrophenoxy group) ), Sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group) Carbamoyl group (unsubstituted carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), amide group (acetamido group, benzamide group, etc.), ureido group (methylureido group, ethylureido group, phenyl Ureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, methoxyethoxycarbonylamino group, etc.), acyl group (acetyl group, benzoyl group, etc.), formyl group, cyano group, carboxy group, sulfo group, hydroxy group, nitro group Groups, alkylthio groups (eg, methylthio group, hydroxyethylthio group, carboxymethylthio group), and arylthio groups (eg, phenylthio group). When there are two or more substituents, they may be the same or different.

R ⁵¹ and R ⁵² , R ⁵¹ and R ⁵³ or R ⁵² and R
^The nitrogen-containing heterocyclic group formed by linking ⁵³ is a saturated or unsaturated 3- to 8-membered ring, which may contain an oxygen atom or a sulfur atom in addition to a carbon atom and a nitrogen atom. It may be condensed with a ring. Specifically, aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, piperazine ring, pyrroline ring, imidazolidine ring, pyrazolidine ring, indoline ring, morpholine ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring, indazole ring , A triazole ring, a tetrazole ring, a phenoxylidine ring, a tetrahydrothiazine ring and the like, and more preferably a saturated or unsaturated 5- or 6-membered ring. Further, these nitrogen-containing heterocyclic rings may have a substituent,
Specific substituents include the same substituents as those described above for R ⁵¹ , R ⁵² and R ⁵³ .

R ⁵¹ and R ⁵² are particularly preferably a hydrogen atom or an alkyl group. As R ⁵³ , an alkyl group is particularly preferable.

Specific examples of the compound represented by the general formula [5] are shown below, but the present invention is not limited thereto.

[0064]

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Other specific examples are described in Japanese Patent Application No. 61-14782.
Compound examples A-1 to A-1 described in pages 3 to 10 of specification 3
2; Compound Example 1 described on pages 10 to 14 of JP-A-61-166674
-(1) to 1- (22); Compound Examples 1- (1) to 1- (21) described in JP-A-61-165621, pp. 11 to 14; Compound examples 1- (1) to 1- (42) described on page 16;
Compound Example 1 on pages 9 to 11 of JP-A-61-170789
(1) to 1- (11); Compound Examples 1- (1) to 1- (24) described in JP-A 61-168159, pp. 11 to 16; Compound Examples 1- (1) to 1- (20) described on page;
Compound Examples 1- (1) to 1- (35) described on page 10, line 4 to page 13, line 2 of JP-A-61-197420;

The compounds represented by the general formula [5] are disclosed in Japanese Patent Application Nos. 61-147823, 61-166674, 61-165621,
No. 61-164515, No. 61-170789, No. 61-168159, No. 61-
It can be obtained by the methods described in 169789 and 61-197420.

The diamine used in the present invention is a compound represented by the following general formula [6].

[0068]

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In the formula, R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. 5] has the same meaning as R ⁵¹ and R ⁵² .

[0070] R ⁶¹ and R ^62, R ⁶³ and R ⁶⁴ and R ⁶² and R ⁶³
May be linked to form a nitrogen-containing heterocyclic ring. Specific examples of the nitrogen-containing heterocyclic ring include R ⁵¹ , R ⁵² and R ⁵¹ of the above general formula [5].
And R ⁵³ or a nitrogen-containing heterocyclic ring formed by linking R ⁵² and R ⁵³ .

R ⁶⁵ represents a divalent organic group, specifically, an alkylene group, an arylene group, an aralkylene group, an alkenylene group or a heterocyclic group. Here, the alkylene group and alkenylene group may be linear, branched or cyclic, and preferably have 1 to 6 carbon atoms, and specifically include a methylene group, a dimethylene group, a trimethylene group, and a methyldimethylene group. , Dimethyl trimethylene group, hexamethylene group, ethylene group, butenylene group,

[0072]

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And the like. These alkylene groups,
The alkenylene group, the arylene group, the aralkylene group, and the heterocyclic group may have a substituent, and specific substituents are the same as the substituents of R ⁵¹ , R ^52, and R ^{53 in} the general formula [5]. And when there are two or more substituents, they may be the same or different.

R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are particularly preferably a hydrogen atom and an alkyl group, and R ⁶⁵ is particularly preferably an alkylene group.

Specific examples of the compound represented by the general formula [6] are shown below, but the present invention is not limited thereto.

[0076]

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[0077]

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Other specific examples are described in Japanese Patent Application No. 61-17359.
Compound Examples 1- (1) to 1- 1 described on page 10 to 13 in the specification of No. 5
(20); Compounds 1- (1) to 1- (42) described in pages 61 to 16 of JP-A-61-164515; Compounds described in pages 11 to 16 of JP-A-61-168159 1- (1) to 1- (24); Compound Examples 1- (1) to 1- (2) described in JP-A-61-169789, pages 9 to 12;
Compounds 1- (1) to 1- (13), 1- (15) and 1- (1) described on page 10, line 4 to page 13, line 6 of JP-A-61-186580.
(19) to 1- (25); and the like.

The compounds represented by the above general formula [6] are described in Japanese Patent Application Nos. 61-173595, 61-164516, 61-168159 and 61-168159.
It can be obtained by the methods described in 169789 and 61-186560.

The amounts of these compounds represented by the general formulas [5] and [6] added to the color developer are preferably from 0.01 g to 100 g, more preferably from 0.1 g to 20 g, per liter of the color developer. It is.

When the color developing solution of the present invention contains a compound represented by the following formula [D] or [E], the solubility of the color developing solution is improved and the effect of improving air oxidation is also improved. The compound is preferably used because it has almost no adverse effect even when mixed in a bleach-fixing solution.

[0082]

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[0083]

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The general formula [D] or the general formula [E] is described in detail in the specification of Japanese Patent Application No. 2-178833, pages 59, 60 and 61. ] Is the same as described above.

Illustrative Compounds of the General Formula [D] D-1-17 Japanese Patent Application No. 2-178833, pages 60-61, C-1.
Same as 17.

Illustrative Compounds of the General Formula [E] E-1 to 33 Japanese Patent Application No. 2-178833, pages 62 to 64, D-1.
Same as 33.

The compound represented by the general formula [D] or the general formula [E] is preferably used in an amount of 1 g to 100 g per liter of the color developing solution, more preferably 2 g to 30 g, from the viewpoint of preventing air oxidation. Used in range.

The color developing solution of the present invention preferably contains a fluorescent whitening agent. The fluorescent whitening agent not only improves the white background performance of the unexposed area of the light-sensitive material, but also has a good effect on the prevention of crystal precipitation when added to the color developing solution of the present invention.

The fluorescent whitening agent is preferably a triazinylstilbene-based compound, and particularly preferably a compound represented by the following formula [F].

[0090]

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The detailed description of the general formula [F] is disclosed in Japanese Patent Application No. 2-1788 / 1990.
It has the same meaning as that of the description of general formula [E] described in page 33, pages 73 to 75 of the specification.

Illustrative compounds of the general formula [F] F-1 to 45: Japanese Patent Application No. 2-178833, pages 76 to 82 E-1:
Same as 45.

The triazinylstilbene-based whitening agent can be synthesized by a usual method described in, for example, “Fluorescent Whitening Agent”, edited by the Chemical Industry Association of Japan, page 8 (issued in August 1976).

Among the exemplified compounds, F-4, F-24, F-34, F-35, F-36 and F-3 are particularly preferably used.
7, F-41.

The amount of the triazinylstilbene-based brightener is preferably in the range of 0.2 to 10 g, more preferably in the range of 0.4 to 5 g per liter of the color developing solution.

Further, if necessary, a color developing solution may be used.
Ethylene glycol, methyl cellosolve, methanol,
Acetone, dimethylformamide, β-cyclodextrin, and other compounds described in JP-B-47-33378 and JP-B-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

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 from 0.01 to 1.0 g / l.

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

It is preferable to add a chelating agent represented by the following general formula [K] to the color developing solution of the present invention from the viewpoint of effectively achieving the object of the present invention.

[0100]

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The detailed description of the general formula [K] is described in Japanese Patent Application No. 2-17 / 1990.
Synonymous with the description of the general formula [K] described in JP-A-8833, pages 84 to 85.

Illustrative Compounds of the Formula [K] K-1 to 22 Japanese Patent Application No. 2-178833, pages 85 to 89, K-1
Same as 22.

Each component of the color developing solution is prepared by adding
It can be prepared by sequentially adding 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 prepared by stirring to prepare a color developing solution of the present invention. Obtainable.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range.
It is preferably 0, and more preferably used at pH 9.8 to 12.0. The processing time is preferably within 3 minutes, more preferably from 3 seconds to 100 seconds, and particularly preferably from 3 seconds to 100 seconds.
It is more than seconds and less than 45 seconds.

In the present invention, the processing temperature of the color developing solution is 30.
The temperature is at least 35 ° C., preferably at least 37 ° C., since the effect of the present invention is particularly remarkable.

In the present invention, when the replenishment amount is low, the effect of the present invention is effectively exhibited.
It is preferably at most 150 ml / m ² , more preferably at most 100 ml / m ² .

In the processing method of the present invention, known processing steps and processing liquids can be employed except for the processing using the color developing solution described above.

Next, preferred photosensitive materials to which the present invention is applied will be described.

The silver halide grains preferably used in the light-sensitive material are silver chloride-based silver halide grains containing at least 80 mol% of silver chloride, more preferably 90 mol% or more, and particularly preferably 95 mol%. The content is more preferably at least 99 mol%.
This is also effective for quickness and prevention of stain. Processing of a light-sensitive material using such a silver chloride emulsion mainly composed of silver chloride is a preferred embodiment of the present invention.

The silver chloride emulsion mainly containing silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less. Is preferably 10 mol% or less, more preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Hereinafter, it is most preferably zero. Such silver chloride 80
Silver halide grains mainly composed of silver chloride consisting of at least
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all silver halide emulsion layers. The crystal of the silver halide grain may be a normal crystal, a twin crystal, or another crystal, and may have [1.0.0] plane and [1.1.1] plane.
Any ratio of surfaces can be used. Furthermore, even though the crystal structure of these silver halide grains is uniform from the inside to the outside, the inside and outside are different in layer structure (core / core).
(Ciel type). These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (JP-A-58-113934, Japanese Patent Application No. 59-113934)
No. 170070) can also be used.

Further, the silver halide grains may be prepared by an acid method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method, further grown by a fast growing ammonia method, and grown to a predetermined size. When growing silver halide grains, controlling the pH, pAg, and the like in the reaction vessel, for example, using silver ions in an amount commensurate with the growth rate of silver halide grains as described in JP-A-54-48521. It is preferable that halide ions are successively simultaneously injected and mixed.

The silver halide emulsion layer of the light-sensitive material processed according to the present invention has a color coupler. These color couplers react with the color developer oxidation products to form non-diffusible dyes. The color coupler is advantageously incorporated in or in close proximity to the photosensitive layer in non-diffusible form.

Thus, the red-sensitive layer can contain, for example, a non-diffusible color coupler for forming a cyan partial color image, generally a phenol or α-naphthol coupler.

The green light-sensitive layer can contain, for example, at least one non-diffusible color coupler for forming a magenta partial color image, usually a 5-pyrazolone-based color coupler and a pyrazolotriazole.

The blue-sensitive layer can contain, for example, at least one non-diffusible color coupler which produces a yellow partial color image, generally a color coupler having an open chain ketomethylene group. The color coupler can be, for example, a 6, 4 or 2 equivalent coupler.

In the present invention, a 2-equivalent coupler is particularly preferred.

Suitable couplers are disclosed, for example, in the following publications: Agfa's work report (Mitteilungln ausde)
n Forschungslaboratorien der Agfa), Leverkusen / Munchen, Vol.II
"Color coupler" (Farbkuppler) by W. Pelz in Ip111 (1964); K. Venkataraman (K. Venkataraman); "The chemistry.
Of Synthetic Soy ”(The Chemirsry of S
synthetic Dyes), Vo1.4, 341-387, Academic Press, "The Theory of the
Photographic Process "(The Theory of Phot
ographic Process), 4th edition, pages 353-362; and Research Disclosure No. 1764
3, section VII.

In the present invention, US Pat. No. 4,310,619
No. 43-51897, European Patent No. 73,636, Research Disclosure No. 24220, No. 24230, JP-A-60-43659 W088
5-pyrazolone and pyrazoloazole compounds described in US Pat.
No.-106655, page 26, a general formula [M
Magenta couplers represented by the following formulas: No. 1 to No. 77 described in JP-A-63-106655, pages 29 to 34, and also page 34. [C-I] or [C-I
I] cyan couplers (specific examples of cyan couplers include (C′-) described in pages 37 to 42 of the same specification.
1) to (C'-82), (C "-1), and (C" -36)), and high-speed yellow couplers also described on page 20 (specific cyan couplers described in the same specification). twenty one
(Y′-1) to (Y′-39) described on page 26 to page 26) are preferred from the viewpoint of the effects of the present invention.

When a nitrogen-containing heterocyclic mercapto compound is used in a light-sensitive material using a silver chloride-based emulsion, not only the effects of the present invention can be obtained well, but also a bleach-fix solution is mixed into a color developing solution. Impact on the photographic performance that occurs when
Since another effect of making it extremely small is exhibited, it can be cited as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds include (I'-1) to (I'-87) described in JP-A-63-106655, pages 42 to 45.

The silver halide emulsion layer mainly containing silver chloride having a silver chloride content of 80 mol% or more can be adjusted by a conventional method (for example, single inflow or double inflow due to constant or rapid acceleration of the material). A particularly preferred method is to adjust the pAg by the double inflow method while adjusting the pAg; Research Disclosure No. 1764
3, see sections I and II.

The silver chloride-based emulsion can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, such as those described in Belgian Patents 493,464 and 56
Silver compounds as described in U.S. Pat.
No. 47,323, polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives. Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization is based on the Zeitschrift Fair
Bissenshaftriche Photography (Z.Wiss.Pho
to.) 46 , 65-72 (1951), in the article by R. Kosiovsky; and also in Research Disclosure No. 17643, Section III above.
See also.

The silver chloride-based emulsion can be prepared by an optically known method,
It can be sensitized using common polymethine dyes, such as, for example, newthocyanines, basic or acidic carbocyanines, rhodocyanines, hemicyanines, styryl dyes, oxonols and the like: FM Hamer. "Cyanine Dyes and Related Compounds" (The Cyanine Dyes and rel
ated Compounds (1964) Ullmanns Enzyk lpa
die der technischen Chemie) 4th edition, volume 18, page 431 and following, and the above-mentioned Research Disclosure No. 176
43, see Section IV.

For the emulsion mainly composed of silver chloride, conventional antifoggants and stabilizers can be used. Azaindene is a particularly suitable stabilizer, preferably tetra and pentaazaindene, especially those substituted with a hydroxyl or amino group. Compounds of this type are described, for example, in Birr's paper, Zeitschrift Vissenshaftriche Photography (Z.Wiss.Photo) 4
7, 1952, pp. 2-58, and Research Disclosure No. 17643, Section IV above.

The components of the light-sensitive material can be contained by a conventional method; for example, US Pat. No. 2,322,027.
Nos. 2,533,514, 3,689,271, 3,764,336 and 3,765,897.

Components of photosensitive material, for example, coupler and UV
The absorbent can also be included in the form of a charged latex; see DE-A 2,541,274 and EP-A 14,921. The components can also be fixed in the light-sensitive material as a polymer;
See 2,044,992, U.S. Patent Nos. 3,370,952 and 4,080,211.

As the support for the light-sensitive material, a conventional support can be used, for example, a support of cellulose ester such as cellulose acetate and a support of polyester. In the context of the present invention, reflective supports, such as paper supports, are most suitable, and they can be coated, for example, with polyolefins, in particular polyethylene or polypropylene; in this regard, see Research Disclosure No. 17643, supra, section VVI. .

As a photosensitive material to which the color developing solution and the processing method of the present invention can be applied, a color paper, a color negative film, a color positive film, and a photosensitive material containing a coupler in the photosensitive material and processed by a so-called internal developing system can be used. It can be applied to any photosensitive material such as a film, a color reversal film for a slide, a color reversal film for a movie, a color reversal film for a TV, and a reversal color paper, but is most preferably applied to a silver chloride-based color paper. is there.

[0130]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 Each layer having the constitution shown on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the other side of the first layer on the other side was coated to form a multilayer color photosensitive material. Created. The coating solution was prepared as described below.

First layer coating solution: 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), and antiirradiation dye (AI-3) 6.5 g of boiling point solvent (DNP)
Was added to 60 ml of ethyl acetate and dissolved, and this solution was added to a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1).
The emulsion was dispersed in 0 ml using an ultrasonic homogenizer to prepare a yellow coupler dispersion. A blue-sensitive silver halide emulsion (containing 10 g of silver) prepared from this dispersion under the following conditions
To prepare a first layer coating solution.

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

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

[0135]

[Table 1]

[0136]

[Table 2]

[0137]

Embedded image

[0138]

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[0139]

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[0140]

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[0141]

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[Method of Preparing Blue-Sensitive Silver Halide Emulsion] 40
(A) in 1000 ml of a 2% aqueous gelatin solution kept at
Solution) and (solution B) while controlling pAg = 6.5 and pH = 3.0.
At the same time, and further add the following (Solution C) and (Solution D)
The co-addition was performed over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

An aqueous solution of sulfuric acid or sodium hydroxide was used for controlling the pH.

At this time, pAg was controlled using a control solution having the following composition. The composition of the control solution is a mixed halide aqueous solution consisting of sodium chloride and sodium bromide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control solution is when mixing the A solution and the B solution. Is 0.1 mol / l, liquid C, D
When mixing the liquid, the amount was 1 mol / liter.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added and 200 ml (Solution B) Silver nitrate 10 g Water was added and 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added and 600 ml (D solution) Silver nitrate 300g Water was added and after the addition of 600ml, desalting was performed using 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. A monodispersed cubic emulsion EMP-1 having a diameter of 0.85 µm, a coefficient of variation (σ / r) = 0.07, and a silver chloride content of 99.5 mol% was obtained.

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

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / mol Molar AgX sensitizing dye (BS-2) 1 × 10 ^-4 mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] (solution A) and (B
Liquid) and the addition time of (Liquid C) and (Liquid D) in the same manner as EMP-1, except that the average particle diameter was 0.43 μm.
m, a coefficient of variation (σ / r) = 0.08 and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5 mol% were obtained.

EMP-2 was reacted with 55
Chemical ripening was performed at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 4 × 10 ⁻⁴ mol / Mol AgX [Method of preparing red-sensitive silver halide emulsion] (solution A) and (B
Liquid) and the addition time of (Liquid C) and (Liquid D) in the same manner as EMP-1 except that the average particle size was 0.5 μm.
m, a coefficient of variation (σ / r) = 0.08 and a monodispersed cubic emulsion EMP-3 having a silver chloride content of 99.5 mol% were obtained.

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

[0151] Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer (STAB-1) 6 × 10- 4 mol / mol AgX Sensitizing dye (RS-1) 4 × 10 -4 mol / Mol AgX

[0152]

Embedded image

The thus prepared color paper sample had a silver chloride content of 99.5 mol%. This sample was exposed according to a conventional method, and then processed using the following processing steps and processing solutions.

Processing Step Processing Temperature Processing Time Replenishment Amount (1) Color Development 38 ± 0.5 ° C. 25 seconds described in Table 8 (2) Bleaching and Fixing 35-37 ° C. 25 seconds 200 ml / m ² (3) Stable (3-tank cascade) 30 -37 ° C 25 seconds 250 ml / m ² (4) Drying 60-80 ° C 30 seconds Color developer tank liquid replenisher Additives listed in Table 3 Diethylhydroxylamine sulfate 3.0 × 10 ^-4 mol 4.0 g Diethylenetriaminepentaacetic acid 1.0 g 1.0 g Potassium chloride 4.0 × 10 ^-2 mol-Potassium bromide 3.0 × 10 ^-4 mol 1.5 × 10 ^-4 mol Potassium sulfite 5.0 × 10 ^-4 mol 1.0 × 10 ^-3 mol Potassium carbonate 30 g 30 g Color developing agent (C- 1) 1.5 × 10 ^-2 mol 2.4 × 10 ^-2 mol Fluorescent bleach (F-34) 1.5 g 1.5 g pH 10.10 10.60 Add water to bring the total volume to 1 liter, and adjust the pH with potassium hydroxide or sulfuric acid. did.

[0155]

Embedded image

Bleach-fixing tank solution and replenisher Ferric ammonium ammonium salt of ethylenediaminetetraacetic acid 0.15 mol Ethylenediaminetetraacetic acid 2.0 g Ammonium thiosulfate 75 g Ammonium sulfite 20 g Ammonium metabisulfite 15 g Glacial acetic acid 15 ml pH 5.35 I do.

[0157] stabilizing tank solution and replenisher o-phenylphenol 0.15g ZnSO ₄ · 7H ₂ O 0.2g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid (60% solution) 3.8 g of ethylenediamine Tetraacetic acid 2.0 g Optical brightener (Tivanol SFP Ciba-Geigy) 2.0 g pH 7.80 Add water to make the total volume 1 liter.

Using the above-described processing steps, a color paper sample prepared by changing the additive of the tank processing liquid as shown in Table 3 was exposed to a wedge and processed.

The maximum color density of yellow (DmaxY) and the γ values (γY, γM, γC) of yellow, magenta, and cyan of the processed color paper sample were measured.

Here, the γ value indicates the gradient between the density point (A) of the minimum density (Dmin) +0.3 and the density point (B) of the minimum density (Dmin) +0.8.

The color balance, which is an effect of the present invention, can be expressed by γY / γM and γC / γM, and it can be said that a value close to 1.0 has excellent color balance.

Table 3 shows the above results.

[0163]

[Table 3]

As is evident from Table 3, when the compound of the present invention is not contained in the color developing solution, the γ value is low and a soft print is obtained, and the color balance is not sufficient as the print quality. On the other hand, when the compound of the present invention was used, it was found that there was an effect in the above-mentioned properties without losing the maximum concentration.

Example 2 Experiment No. 1 was carried out using the sample prepared in Example 1 by changing the amount of potassium sulfite in the color developing tank solution as shown in Table 4.
With respect to -1, 1-3, 1-6, and 1-9, the same evaluation as in Example 1 was performed.

Table 4 shows the results.

[0167]

[Table 4]

As apparent from Table 4, the sulfite was 3 × 10 ^-3.
When the molar ratio is more than mol / l, the γ value is lowered, the color tone becomes soft, and the color balance is deteriorated. Thus, the effect of the present invention is lost.

Example 3 The amount of potassium chloride in the color developing tank solution was changed as shown in Table 5, and the sample prepared in Example 1 was used.
For 1,1-3,1-6,1-9, the same evaluation as in Example 1 and the evaluation of the minimum yellow density (DminY) were performed.

Table 5 shows the results.

[0171]

[Table 5]

As is clear from Table 5, in the present invention, when the amount of chloride is 3 × 10 ^-2 mol / l or more, the effect of lowering the minimum concentration becomes remarkable in addition to the effect of the present invention.

Example 4 Experiment Nos. 1-1 and 1-9 were performed using the samples prepared in Example 1 with the preservatives shown in Tables 6 and 7 in place of diethylhydroxylamine in the color developing tank solution. Example 1
The same evaluation was performed.

Tables 6 and 7 show the results.

[0175]

[Table 6]

[0176]

[Table 7]

As is clear from Table 6, when at least one compound represented by the general formulas [2] to [6], Tables 6 and 7 is added in the present invention, the effect of the present invention becomes more remarkable, It can be seen that the effect of the compound represented by the formula [1] is increased.

Example 5 A running process was performed using the sample and the processing steps prepared in Example 1. In the running process, continuous processing was performed at 0.05R per day until the amount of the color developing solution replenished in the color developing tank solution became three times the volume of the color developing tank solution.

Incidentally, 1R means that the replenishment of color development for the capacity of the color development tank is replenished.

Table 8 shows the results of the same evaluation as in Example 1 at the end of running and at the start of running, with the replenishment amount of the color developing solution and the processing temperature varied as shown in Table 8.

[0181]

[Table 8]

As is clear from Table 8, when the compound of the present invention was contained in the running treatment, the maximum concentration was stable and the fluctuation of the γ value was extremely small.

Further, in the present invention, when the replenishment rate of the color developing solution is 150 ml / m ² or less, preferably 100 ml / m ² or less, and when the processing temperature of the color developing solution is 35 ° C. or more, the effect of the present invention is more remarkable. It turns out that it becomes.

Example 6 Table 9 shows the results of the same evaluation as in Example 5, except that the processing was performed using the following processing steps and a color developing solution.

Processing Step Processing Temperature Processing Time Replenishment Amount (1) Color Development Listed in Table 9 160 ml / m ² (2) Bleaching and Fixing 35-37 ° C. 1 minute 200 ml / m ² (3) Stable (3-bath cascade) 30-37 2 minutes at 200 ° C / m ² (4) Drying 60 to 80 ° C for 2 minutes-Color developing tank solution (1 liter) Replenisher (1 liter) Additives (Table 6) Table 9 Potassium bromide 5 × 10 ^-3 mol 5 × 10 ^-3 mol Potassium chloride 1.5 × 10 ^-1 mol 1.5 × 10 ^-1 mol Potassium sulfite 5.0 × 10 ^-4 mol 1.0 × 10 ^-3 mol Color developing agent (C-1) 1.5 × 10 ^-2 mol 2.4 × 10 ^-2 mol Diethylhydroxylamine 3.5 × 10 ^-2 mol 5.0 × 10 ^-2 mol Sulfate triethanolamine 7.0 g 10.0 g Potassium carbonate 30.0 g 30.0 g Diethylenetriamine pentaacetic acid 1.0 g 1.0 g pH 10.10 10.60

[0186]

[Table 9]

As is clear from Table 9, the effect of the present invention is remarkable even when the processing time is long.

[0188]

As described above, according to the present invention, it is possible to provide a processing solution capable of obtaining a gradation suitable for color printing and capable of performing stable processing, and a processing solution and a processing method with little processing fluctuation.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/407

Claims (3)

(57) [Claims] 1. A paraphenylenediamine-based color developing agent
And a compound represented by the following general formula [1], and
When sulfite is less than 3.0 × 10 ^-3 mol per liter
Silver developer containing no color developing solution
Halo having silver halide grains containing at least 80 mol%
A silver gemide color photographic material is processed at a processing temperature of 35 ° C or higher.
The replenishment amount of the color developing solution is determined by silver halide color photographic exposure.
And wherein the processing as follows material 1 m ² per 150ml
For processing silver halide color photographic light-sensitive materials. Embedded image [In the formula, Z ₁ represents an atomic group necessary for forming a benzene ring or a nitrogen-containing 6-membered hetero ring, and Z ₂ represents a group necessary for forming a pyrazole ring, an imiazole ring or a triazole ring together with -NH-. Represents an atomic group. ] Wherein according to the color developing solution is characterized by containing a chloride 3.0 × 10 ^-2 mol per liter
Item 1. Processing method of silver halide color photographic light-sensitive material according to item 1.
Law. 3. The color developer according to claim 1, wherein the color developer contains at least one compound selected from the group consisting of hydroxylamine derivatives, hydrazines, hydrazides, α-hydroxyketones, α-aminoketones, monoamines and diamines. 3. The silver halide color according to claim 1, wherein
Processing method of photographic photosensitive material .