JPH11265046A - Color image forming method and desilvering composition to be used for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color image forming method superior in color reproduction and improved in residual agent stains due to easy rapid processing in the color image forming process for obtaining an image after image exposure through development processing. SOLUTION: The silver halide color photographic sensitive formed by laminating each one of yellow, magenta, and cyan color developing emulsion layers and one nonphotosensitive hydrophilic colloidal layer on a support is subjected to image exposure and development and desilvering and rinsing and/or stabilizing processes and drying in this color image forming method. One of this desilvering and rinsing and/or stabilizing processes is operated in the presence of a compound represented by the formula in which each of R<1> and R<2> is an H atom or an alkyl group and the total carbon number of them is an integer of 3-8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide color photographic light-sensitive material. The present invention relates to a color image forming method which is excellent in rapid processing property, has less stain during image storage, and has excellent storage stability of a bleach-fixing composition.

[0002]

2. Description of the Related Art Development processing of silver halide color photographic light-sensitive materials, especially ornamental light-sensitive materials such as light-sensitive materials for printing, has a high productivity. There is an increasing demand for simple (simplified and quick) maintenance of the processing. For this reason, the productivity is improved by continuously performing the developing process with an automatic developing machine such as a mini lab while replenishing the developing solution in a liquid form or a solid content form in order to maintain the processing performance.
In general, conditions for harmonizing development processing are more severe in order to maintain stable development processing performance, and there is a need for a technique for providing a more stable and higher-quality color image in conventional simple processing than before. Have been.

In a color image of a silver halide color photographic light-sensitive material, a dye is formed by a reaction of a color developing agent oxidized with an exposed silver halide as an oxidizing agent with a coupler. In such a dye forming method, the fatigue deterioration of the processing solution due to a reduction in the development processing time or a reduction in waste liquid causes a change in color density or an increase in sensitivity change,
It is known that the image storability after processing is deteriorated. Deterioration of image preservability is caused by an increase in the amount of developing agent accumulated in the bleach-fixing solution or the washing or stabilizing solution and a reduction in processing time, resulting in an increase in residual agent in the photosensitive material. It is known that a part is colored (this coloring is hereinafter referred to as a residual principal stain).

[0004] As a technique for preventing an increase in the amount of a residual active substance in the above-mentioned development processing, for example, JP-A-8-30498
Monoguanidines described in No. 0, JP-A-5-3031
No. 85 describes a method of using an amidine or a bisguanidine as a treatment solution. However, these conventional compounds used in the processing solution are not always sufficiently effective to improve the residual active ingredient stain, have a problem of deteriorating the resolution during image storage, and tend to deteriorate image sharpness after storage under moist heat ( However, sufficient compounds have not always been known, for example, there are problems with the stability of the replenisher such as the occurrence of precipitation when the replenisher is stored.

On the other hand, phenol or naphthol-based couplers have been conventionally used as couplers used for forming cyan dye images of photosensitive materials for printing.
However, the dyes formed from these couplers have an unfavorable absorption in the yellow to magenta region, and thus have a problem of deteriorating color reproducibility. Was rare.
U.S. Pat.
Heterocyclic compounds described in 8,598, 4,873,183, European Patent Application Publication No. 0249453A2 and the like have been proposed. However, these couplers have disadvantages such as low coupling activity and poor dye fastness.

The pyrrolotriazole couplers described in US Pat. No. 5,256,526 and European Patent No. 0545300 are characterized by excellent color reproducibility and high color development due to high coupling activity. However, on the other hand, the pyrrolotriazole coupler also has a problem that the residual principal agent stain is more likely to be deteriorated than the conventional phenol or naphthol coupler when a treatment in which the residual principal agent is easily increased such as a simple rapid treatment. Further, a method of suppressing the stain caused by the remaining main drug by dispersing and using a certain type of the main drug capturing agent together with the coupler is disclosed in, for example, EP 544317. It is known that such a principal agent capturing agent has an effect of preventing a coupling reaction between an unreacted coupler and the residual principal agent by reacting with the residual principal agent or its oxide. However, at present, it is impossible to prevent stain in the case of simple and rapid treatment in which the amount of the remaining active ingredient exceeds the practical use amount of these stain inhibitors, and especially in the case of pyrrolotriazole couplers having a high coupling activity, an improvement means is necessary. Had been requested.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color image forming method in which an image is exposed through a development process after an imagewise exposure of a silver halide color photographic light-sensitive material, and excellent color reproduction is obtained. It is an object of the present invention to provide a color image forming method in which the residual principal stain is improved by simple and rapid processing.

[0008]

Means for Solving the Problems As an effective means for solving the above-mentioned problems, the present inventor has found a method for removing a residual principal agent during treatment by using a treatment solution containing a specific guanidine compound. That is, the object of the present invention is attained by providing a color image forming method having the following constitutions (1) to (7) and a composition for desilvering treatment used therefor. (1) a support having at least one layer each of a yellow color-forming photosensitive silver halide emulsion layer, a magenta color-forming photosensitive silver halide emulsion layer, and a cyan color-forming photosensitive silver halide emulsion layer on a support; A silver halide color photographic light-sensitive material having at least one non-color-forming hydrophilic colloid layer, which is subjected to image exposure, followed by development, desilvering, washing with water and / or stabilization, followed by drying. A color image forming method, wherein at least one of the steps of desilvering, washing and / or stabilizing is performed in the presence of a compound represented by the following general formula [A].

Embedded image In the formula [A], R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an aralkyl group. The total number of carbon atoms of R ¹ + R ² is 3-8, and R ¹ and R ² are not simultaneously hydrogen atoms, R ¹ and R ² may form a ring bonded to each other. (2) The color image forming method as described in (1) above, wherein the desilvering treatment is performed in the presence of the compound represented by the general formula [A]. (3) The above (1) or (1), wherein at least one of the cyan coloring light-sensitive silver halide emulsion layers contains at least one cyan dye-forming coupler selected from the compounds represented by the following general formula (I). The color image forming method according to (2).

Embedded image Wherein ^{(I), Z a, Z} b each -C (R ⁵⁾ = or represents -N =. However, either Z ^a or Z ^b is −
Is N =, the other is -C (R ⁵⁾ is =. R ³ and R
⁴ has a Hammett's substituent constant σ _p value of 0.20
Represents the above electron-withdrawing group, and the sum of the σ _p values of R ³ and R ⁴ is 0.65 or more. R ⁵ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. The group of R ³ , R ⁴ , R ⁵ or X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. (4) at least one layer of cyan-color-forming photosensitive silver halide emulsion layer, or at least one layer of the non-color-forming hydrophilic colloid layer, or at least one layer of cyan-color-forming photosensitive silver halide emulsion layer and the non-color-forming hydrophilic layer The color image forming method according to any one of the above (1) to (3), wherein at least one of the colloid layers contains at least one compound represented by the following general formula (II).

Embedded image In formula (II), R ^a1 and R ^a2 each independently represent a hydrogen atom, an alkyl group or an aryl group. R ^a3 and R ^a4 represent a hydrogen atom,
Represents an alkyl group or an aryl group. R ^a5 represents an aryl group. However, ^Ra1 , ^Ra2 , ^Ra3 , ^Ra4 and ^Ra5
Does not become 13 or less. (5) The color image forming method as described in any one of (1) to (4) above, wherein the silver halide emulsion is a high silver chloride emulsion having a silver chloride content of 95 mol% or more. (6) The color image forming method according to any one of the above (1) to (5), wherein the exposure is performed by scanning exposure. (7) A processing composition for desilvering a silver halide color photographic light-sensitive material, characterized by containing at least one compound represented by the formula [A].

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the outline of the processing steps of development, desilvering, washing with water and / or stabilization in the color image forming method of the present invention will be described.

[Development] The color developing solution usable in the developing step of the present invention is described in JP-A-3-33847, page 9, line 6 in the upper left column to line 6 in the lower right column of page 11. And those described in JP-A-5-197107. As the color developing agent in the color developing step, a known aromatic primary amine color developing agent can be used, and p-phenylenediamine compounds are preferably used. A typical example thereof is 3-methyl-4-amino acid. -N, N diethylaniline, 3-methyl-4-amino-N-ethyl-N- β-
Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N
-(3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-propyl
-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N -(4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl
-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-
Hydroxypentyl) aniline, 4-amino-3-methyl-N
-(5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, Examples include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among them, in particular, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose.

[0011] European Patent Publication No. 410450,
Those described in -11255 and the like can also be preferably used. In addition, these p-phenylenediamine derivatives and salts such as sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, and p-toluenesulfonic acid may be used. The amount of the aromatic primary amine developing agent to be used is preferably 0.0002 mol to 0.2 mol, more preferably 0.001 mol to 0.1 mol, per liter of the color developer.

In the color developer, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfites such as potassium bisulfite, sodium metasulfite, and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

An optional development accelerator can be added to the color developer if necessary. Examples of the development accelerator include thioether compounds described in U.S. Pat. No. 3,813,247 and JP-A-52-49829 and JP-A-50-1555.
4, quaternary ammonium salts described in JP-B-44-30074, U.S. Pat. Nos. 2,482,546, and 2,59.
Amine compounds described in US Pat. No. 6,926 and 3,582,346, polyalkylene oxides described in U.S. Pat. No. 3,532,501, etc., other 1-phenyl-3-pyrazolidones, imidazoles , Etc. can be added as needed.

In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ′, N′-tetramethylenephosphonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether terdiaminetetraacetic acid, ethylenediamine orthohydroxyphenyl acid, 2-phosphonobutane-1,2- , 4-Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, -N'-bis (2-hydroxybenzyl) ethylenediamine-N,
N'-diacetate hydroxyethyliminodiacetic acid and the like. These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, about 0.1 g to 10 g per liter,

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, And nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adanine.

In the present invention, the color developer preferably contains 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter of chloride ions. Particularly preferably 3.5 × 10 ^-2.
Mol / l to 1.0 × 10 ^-1 mol / l. If the chloride ion concentration is more than 1.5 × 10 ⁻¹ mol / l, it has the disadvantage of delaying the development, and is not preferred for achieving the object of the present invention, which is rapid and has a high maximum concentration. If the concentration is less than 3.0 × 10 ^-2 mol / liter,
It is not preferable in preventing fog. In the present invention,
It is preferable that the color developer contains bromine ions in an amount of 0.5 × 10 ⁻⁵ mol / l to 1.0 × 10 ⁻³ mol / l. More preferably, 3.0 × 10 ^{−5 to} 5 × 1
^0-4 mol / l. Bromine ion concentration is 1 × 10
^{When the amount is} more than ^-3 mol / l, the development is delayed and the maximum density and the sensitivity are lowered. When the amount is less than 0.5 × 10 ^-5 mol / l, fog cannot be sufficiently prevented.

Here, the chloride ions and bromine ions may be added directly to the color developer, or may be eluted from the photosensitive material into the color developer during the development processing. When directly added to a color developer, examples of the chloride ion supplying material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride, and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developer. Examples of the bromine ion supply material include sodium bromide, potassium bromide / ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

It is preferable that the color developing solution used in the developing step of the present invention does not substantially contain benzyl alcohol. Here, "substantially not contained" means preferably 2 ml / liter or less, more preferably 0.5 ml / liter or less.
It has a benzyl alcohol concentration of 1 / liter or less, most preferably no benzyl alcohol at all.

The color developer used in the present invention must be substantially free of sulfite ions in order to suppress fluctuations in photographic characteristics due to continuous processing and to achieve the effects of the present invention (here, substantially free of sulfite ions). If not, the sulfite ion concentration is preferably 3.0 × 10 ⁻³ mol / L or less.) Preferably, it contains no sulfite ion at 1.0 × 10 ⁻³ mol / l or less, most preferably no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded. The color developer used in the present invention should be substantially free of hydroxylamine in order to suppress a change in characteristics due to a change in the concentration of hydroxylamine. .0
× 10 ^-3 mol / liter or less. Is more preferred. Most preferably it contains no hydroxylamine.

The color developer used in the present invention preferably has a pH of 9 to 13, and more preferably 9 to 12.5. The color developer contains other known developer component compounds. be able to. In order to maintain the above pH, it is preferable to use various buffer materials.

Specific examples of these buffer materials include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. The amount of the buffer added to the color developer is preferably 0.1 mol / L or more, and particularly preferably 0.1 mol / L to 0.1 mol / L.
Particularly preferred is 4 mol / l.

The processing temperature of the color developing solution in the present invention is from 20 to 55 ° C., preferably from 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 3 seconds for the photographic material.
0 second to 3 minutes and 20 seconds. More preferably, 1 minute to 2 minutes 3
0 seconds, and 10 seconds to 60 seconds for printing materials.
Seconds, preferably 10 seconds to 45 seconds, more preferably 10 seconds to 30 seconds.

[Desilvering Step] Next, the desilvering process will be described. The present invention is characterized in that in the desilvering step and at least one of the washing and / or stabilizing treatment steps described below, the above-mentioned general formula [A], which will be described in detail later, is added as a principal agent removal accelerator. And In the desilvering process, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). The aspect of the desilvering step in the present invention is preferably a bleach-fixing treatment for the purpose of simplifying the step and shortening the time. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. The desilvering step is generally performed by combining a bleaching step, a bleach-fixing step, and a fixing step.

As the bleaching agent for the processing solution having bleaching ability,
For example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Representative bleaching agents include organic complexes of iron (III), for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4-121739, page 4
Bleaching agents including iron complex salts of 1,3-propylenediaminetetraacetate from the lower right column to the upper left column on page 5;
Carbamoyl bleach described in U.S. Pat. No. 73647, bleach having a heterocycle described in JP-A-4-174432,
Bleaching agents described in EP-A-520457, including ferric N- (2-carboxyphenyl) iminodiacetic acid complex salt, ethylenediamine-N-2-carboxyphenyl-N, N ', N'-triacetic acid Bleaching agents described in European Patent Publication No. 530828A1, bleaching agents described in European Patent Publication No. 501479, bleaching agents described in European Patent Publication No. 567126, including ferric acetic acid;
Bleaching agent described in JP-A-127145;
The ferric salt of aminopolycarboxylic acid or the salt thereof described on page (11) of JP-A No. 46 can be exemplified, but not limited thereto.

In the bleaching solution, the bleach-fixing solution and their prebaths, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators include US Pat.
No. 93,858, Research Disclosure No.
Compounds having a mercapto group or a disulfide bond described in, for example, No. 17129 (July, 1978);
Thioazolidine derivatives described in U.S. Pat. No. 0,140,129; thiourea derivatives described in U.S. Pat. No. 3,706,561;
Iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, US Pat.
No. 8, West German Patent No. 1,290,812,
Compounds described in No. 95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.

The bleaching solution or bleach-fixing solution according to the present invention further comprises a bleaching accelerator, a corrosion inhibitor for preventing the corrosion of the processing bath, a buffer for maintaining the pH of the solution, a fluorescent whitening agent, an antifoaming agent and the like. It is added as needed. Regarding the bleaching accelerator, for example, US Pat. No. 3,893,858,
German Patent 1,290,821, British Patent 1,138,842, JP-A-53-95630
And compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July 1978), JP-A-50-140129
Thiazolidine derivatives described in U.S. Pat.
No. 06561, thiourea derivatives, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, JP-B-45-8636. And the like. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferably, British Patent 1,138,8
Mercapto compounds described in JP-A-42-190, JP-A-2-190856 are preferred.

It is preferable that the bleaching solution and the bleach-fixing solution contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5.5, and specifically, acetic acid, propionic acid and the like. As the corrosion inhibitor, a nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate and the like are used.
The addition amount is 0.01 to 2.0 mol / l, preferably 0.05 to 0.5 mol / l.

In recent years, awareness of the preservation of the global environment has increased, and efforts have been made to reduce nitrogen atoms discharged into the environment. From such a viewpoint, it is desired that the treatment liquid of the present invention does not substantially contain ammonium ions. In the present invention, the phrase "contains substantially no ammonium ion" means that the concentration of ammonium ion is 0.1.
1 mol / liter or less, preferably 0.0
8 mol / l or less, more preferably 0.01 mol / l
1 liter or less, particularly preferably a state in which it is not contained at all. In order to reduce the ammonium ion concentration in the range of the present invention, alkali metal ions and alkaline earth metal ions are preferable as alternative cation species, and alkali metal ions are particularly preferable, and lithium ion, sodium ion and potassium ion are particularly preferable. However, specifically, sodium salts and potassium salts of a ferric organic acid complex as a bleaching agent, potassium bromide as a rehalogenating agent in a processing solution having bleaching ability, sodium bromide, potassium nitrate, Sodium nitrate and the like. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferred.

The pH of the bleaching solution or bleach-fixing solution of the present invention is 2.0 to 8.0, preferably 3.0 to 7.5. The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since the photographic performance is extremely stably maintained. The bleaching or bleach-fixing process
It can be carried out in a temperature range of 30 ° C to 60 ° C, preferably 35 ° C.
C. to 50C.

The light-sensitive material processed with a processing solution having bleaching ability is subjected to fixing or bleach-fixing processing. When the processing solution having the bleaching ability is a bleach-fixing solution, a fixing or bleach-fixing process may or may not be performed thereafter. Such a fixing solution or a bleach-fixing solution is also disclosed in JP-A-3-33847.
It is preferable to use those described on page 6, lower right column, line 16 to page 8, upper left column, line 15.

As a fixing agent in the desilvering step, ammonium thiosulfate has generally been used, but other known fixing agents, for example, mesoionic compounds, thioether compounds, thioureas, a large amount of iodide, hypo, etc. May be replaced by These are disclosed in JP-A-60-61749,
Nos. 60-147735, 64-21444, JP-A-1-201659, 1-
Nos. 210951, 2-44355 and U.S. Pat. No. 4,378,424. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,8-octanediol, imidazole and the like. No. Of these, thiosulfates and mesoions are preferred. Ammonium thiosulfate is preferred from the viewpoint of quick fixability. However, as described above, sodium thiosulfate and meso ions are more preferred from the viewpoint of substantially eliminating ammonium ions from the processing solution due to environmental problems. Furthermore, by using two or more types of fixing agents in combination, it is possible to perform quicker fixing. For example, it is preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like in addition to ammonium thiosulfate and sodium thiosulfate. It is preferably added in the range of 01 to 100 mol%.

The amount of the fixing agent is bleach-fixing solution or fixing solution 1
0.1 to 3.0 mol per liter, preferably 0.5 to
2.0 moles. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to 9.0, and particularly when thiosulfate is used, 5.8 to 8.0 provides stable fixing performance. Preferred above.

A preservative is added to the bleach-fixing solution or the fixing solution,
The temporal stability of the liquid can also be improved. In the case of a bleach-fixing solution or a fixing solution containing a thiosulfate, a sulfite and / or a bisulfite adduct of hydroxylamine, hydrazine or aldehyde (for example, a bisulfite adduct of acetaldehyde, particularly preferably Is effective to use an aromatic aldehyde bisulfite adduct described in JP-A-1-298935.

In the present invention, the bleach-fixing solution or fixing solution containing the compound of the formula [A] preferably contains at least one sulfinic acid and a salt thereof. The amount of sulfinic acid and its salt to be added to the bleach-fixing solution or the fixing solution is 1 to 1 liter of the processing solution.
× 10 ^-4 to 1 mol, more preferably 1 × 10 ^{-3 to} 0.5
Mole, more preferably 1 × 10 ^{-2 to} 0.1 mole.

In the present invention, the bleaching / fixing step
Total silver processing time is desilvered for the purpose of shortening processing time
It is preferable that the length is short as long as no defect occurs. Preferred time
Is 5 seconds to 1 minute, more preferably 5 seconds to 25 seconds.
is there. The processing temperature is 25 ° C to 50 ° C, preferably 3 ° C.
5 ° C to 45 ° C. In the preferred temperature range,
Improved silver speed and effective generation of stain after processing
Is prevented. In addition, each of the above-mentioned processing solutions used in the present invention is
For example, Japanese Patent Application Laid-Open No. 62-183460
Emulsions described in Examples on page 3, lower right column to page 4, lower right column
From a slit or nozzle provided facing the surface
Applying the method of discharging the liquid pumped by the pump
Can be. Further, the treatment of the present invention is based on the liquid aperture ratio (air contact).
Contact area (cm^Two) / Liquid volume (cm ^Two)] Is any state
But relatively better performance than combinations other than the present invention
However, from the viewpoint of the stability of the liquid component, the liquid aperture ratio is
0-0.1cm^-1Is preferred. In continuous processing,
0.001cm^-1~ 0.05cm^-1Good range
Preferably, more preferably 0.002 to 0.03 cm^-1
It is.

[Washing and / or Stabilization] Next, the washing and / or stabilizing steps in the color image forming method of the present invention will be described. By adding the compound of the general formula [A] of the present invention to the washing water and / or the stabilizing solution, the effect of accelerating the removal of the principal agent can be obtained as in the case of adding to the desilvering step. A processing method in the washing and / or stabilizing step is disclosed in JP-A-57-8543.
, 58-14834 and 60-220345 can all be used. Also,
A washing step-stabilizing step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Various surfactants can be contained in the washing water or the stabilizing solution used in the washing and / or stabilizing step in order to prevent unevenness of water droplets when the processed photosensitive material is dried.
These surfactants include polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant Agent, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino acid type amphoteric surfactant, betaine type amphoteric surfactant Since the ionic surfactant may combine with various ions mixed in with the treatment to form an insoluble substance, it is preferable to use a nonionic surfactant, and in particular, an alkylphenol ethylene oxide adduct is preferably used. preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferred as alkylphenols, and the number of moles of ethylene oxide added is particularly preferably 8 to 14 mol. It is also preferable to use a silicon surfactant having a high defoaming effect. In the stabilizing solution, an aldehyde such as formalin or glutaraldehyde, an N-methylol compound, hexamethylenetetramine, or an aldehyde sulfite adduct can be used as a dye stabilizer. In addition, the stabilizing solution may further contain a pH adjusting buffer such as boric acid or sodium hydroxide; 1-hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid; a sulfuric acid such as alkanolamine. An inhibitor, a fluorescent whitening agent, a fungicide, and the like can be contained.

In the washing water or the stabilizing solution, various antibacterial agents and fungicides can be contained for preventing generation of water rust and mold generated on the photosensitive material after processing. Examples of these antibacterial agents and fungicides include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, and JP-A-54-27424 and JP-A-54-27424. Kaisho 57
No. 8542, isothiazolone compounds, or chlorophenol compounds represented by trichlorophenol, or bromophenol compounds, or organotin or organozinc compounds, or thiocyanic acid or isothiocyanic acid compounds Compounds, or acid amide compounds, or diazine or triazine compounds, or thiourea compounds, benzotriazole alkylguanidine compounds, or quaternary ammonium salts such as benzalkonium chloride, or penicillin Antibiotics such as those represented by Journal Antibacterial and Antifangus Agent (J. Antibact.A
ntifung.Agents) Voll. No. 5, p.207-223 (1
983) may be used in combination of one or more. Also, various germicides described in JP-A-48-83820 can be used. Further, as a solution to the problems such as the propagation of bacteria and the adhesion of generated suspended matter to the photosensitive material, which occur when the amount of washing water is significantly reduced in the multi-stage countercurrent method, the method described in Japanese Patent Publication No. 62-288838 is disclosed. A method for reducing calcium ions and magnesium ions can be used very effectively.

It is preferable to use various chelating agents in combination as long as the effects of the compound of the present invention are not impaired.
Preferred compounds of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediamine-N, N, N ', N'-.
Examples thereof include organic phosphonic acids such as tetramethylene phosphonic acid, and hydrolysates of a maleic anhydride polymer described in EP 345172 A1. Further, it is preferable that a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution is contained in the washing water. As water used in these washing steps or stabilizing steps,
In addition to tap water, it is preferable to use water deionized to a Ca or Mg concentration of 5 mg / liter or less with an ion-exchange resin or the like, water sterilized by halogen, an ultraviolet germicidal lamp, or the like.

The pH of the washing water is 4-9, preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally 15 to 45 ° C.
For 10 seconds to 5 minutes, preferably for 10 seconds to 9 at 35 to 45 ° C.
A range of 0 seconds is selected. The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.
In the present invention, water washed and / or stabilized with a reverse osmosis membrane can be effectively used. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate and the like can be used.

The liquid sending pressure in the use of these membranes is preferably from ^{2 to} 10 kg / cm ² , and particularly preferably from 3 to 7 in order to prevent stain and to prevent a decrease in the amount of permeated water.
Kg / cm ² . The washing and / or stabilizing step is preferably connected to a multi-stage countercurrent system using a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks.

The processing method of the present invention is effective in any processing method for developing a light-sensitive material containing a silver halide emulsion, but contains a high silver chloride emulsion having a silver chloride content of 95 mol% or more. This is particularly effective when the color photographic paper is processed in a low-speed refill process. The high silver chloride emulsion preferably comprises silver chlorobromide or silver chloride having a silver chloride content of 98 mol% or more.

In the present invention, the replenishing method of the developing step, desilvering step, washing and / or stabilizing step is not limited to replenishing a replenisher of a single composition, but also replenishing a plurality of replenishers of a plurality of compositions. In the case of separate replenishment, the replenishment can be carried out by any method of replenishment of one or more replenishers or water and the addition of a solid substance composed of replenishing components. In the present invention, the replenishment amount per step is represented by an increase in volume when these are replenished when they are separately replenished into a plurality of replenishers, and a single or a plurality of replenishers or water is replenished. Separation between the replenishment and the addition of the solid material comprising the replenishment components is also represented by the increase in volume when they are replenished.

[0043] The low replenishment rate of the processing in the present invention varies depending on the kind of the photosensitive material, for example, in the case of development processing for color printing, replenishing amount per photosensitive material 1 m ² is
The replenishment amount of the color developing solution is 10 to 60 ml / m ² , more preferably 20 to 45 ml / m ² , and at the same time, the replenishment amount of the bleach-fix solution is 20 to 50 ml / m ² , and washing with water and / or stabilization. Replenishment rate of liquid is 50-100ml / m
It is preferably ² . Also,. At this time, the total replenishment amount in all the steps is preferably 70 to 200 ml / m ² , and 90 to 200 ml / m ^2.
160 ml / m ² is more preferred.

In the present invention, continuous processing refers to processing of a light-sensitive material which requires substantial replenishment of a processing solution. More specifically, it refers to performing a development process in which the replenishment amount accompanying the color print process is equivalent to 0.1 to 20% of the capacity of the processing tank as an average per day for a plurality of days. In particular, conditions under which the effects of reducing stains and stabilizing photographic performance in simple and rapid processing can be obtained are such that the average replenishment amount per day is preferably 0.1 to 20% of the capacity of the developing tank, and more preferably 0 to 20%. 0.2 to 10%, most preferably 0.5 to 6%.
At this time, the capacity of the color developing tank is not particularly limited, but is usually 50 liters or less, preferably 0.2 to 20 liters, and most preferably 1 to 10 liters. Also,
The processing amount is determined by the replenishment amount per 1 m ² of the photosensitive machine charge and the average replenishment amount per day. Specifically, in the case of a photosensitive material for color printing, the average amount is 0.1% per day.
It is preferably 1~80m ^2, more preferably 0.2~6060m ^2, most preferably 0.1 to
30 m ² .

To speed up the processing in the present invention means to shorten the time required for developing an exposed photosensitive material and obtaining an image through a drying step. Specifically, by shortening one or more of the color developing step, desilvering step, washing and / or stabilizing step, and drying step, all the processing steps are performed for 30 to 90 seconds, preferably 50 to 90 seconds. Seconds is a preferred embodiment of the present invention. In each processing step, the processing time in the developing step and the processing time in the desilvering step are each preferably 30 seconds or less, and more preferably 10 to 15 seconds. At this time, the ratio (Tw / Tbf) of the processing time (Tw) of the washing and / or stabilizing step to the processing time (Tbf) of the bleach-fixing step is preferably 1.3 or less. In the present specification, the ultra-rapid processing refers to processing a photosensitive material containing a silver halide emulsion having a silver chloride content of 95 mol% or more in all processing steps in the above-mentioned time.

The processing time of the step in the invention does not mean the time required from the start of processing of the photosensitive material in one step to the start of processing in the next step. In the present invention, the beginning of the developing step means when the photosensitive material is immersed in the color developing solution, and the end of the drying step means when the photosensitive material has passed through the final transport roller in the drying step.

The actual processing time of an automatic processor usually depends on the linear velocity and the capacity of the processing bath. As a standard of the linear velocity in the present invention, 500 to 4000 mm /
In particular, in the case of a small developing machine called a minilab, the speed is preferably 500 to 2500 mm / min.

In the present invention, the washing and / or stabilizing treatment is preferably carried out in a multi-stage countercurrent bath. At this time, it is more preferred that the photosensitive material be moved between the tanks in the liquid so as not to come into contact with air. . As a method of moving between the tanks in the liquid, for example, a photosensitive material passage is provided between the tanks, and the passage can be opened and closed by shutter means. At this time, it is preferable that a pair of flexible blades is provided as the shutter means so that only the leading ends of the blades elastically contact each other.

In the present invention, at least one of the steps of development, desilvering, washing with water and / or stabilization is preferably carried out in the presence of a diaminostilbene-based optical brightener. As the diaminostilbene-based fluorescent whitening agent, specifically, compounds described in Tables 1 to 6 of JP-A-6-332127 are preferable, and among these, the compound (SR-
1) to (SR-16) are particularly preferred. The diaminostilbene-based fluorescent whitening agent can be contained in both the light-sensitive material and the processing solution, but is preferably contained in the processing solution.
It is preferably contained in any one of the processing solutions of (2) desilvering and (3) water washing and / or stabilization, but is preferably substantially contained in the processing solution of a plurality of steps. Here, the desilvering step includes any one of bleaching / fixing and bleach-fixing steps and a combination thereof.

In the present invention, as described above, the spraying amount of the circulating treatment liquid is usually 1 liter / min or more and 10 liter /
Minutes or less. The circulation amount is 1 to achieve the above spray amount.
１５15 liters / min, preferably 2 to 10 liters / min, which is equal to or greater than the spray amount. The circulation amount and the spray amount may be the same. In the present invention, it is necessary that this condition is satisfied at least when the photosensitive material is being processed. This condition may be satisfied when the power of the processing machine is turned on. The circulating and spraying may be either in a form of circulating in the processing tank or in a form in which the circulating liquid is sprayed on the photosensitive layer side of the photosensitive material. In the present invention, the circulating liquid is sprayed on at least the photosensitive layer side of the photosensitive material. Spraying is preferably in liquid. The circulating liquid is filtered through a filter by a conventional method, and then returned to the treatment tank. The spray amount of the circulation treatment liquid is preferably 2. ~ 7 l / min. The circulation amount of the processing liquid is preferably 0.5 to 20 liters / minute per one processing tank, more preferably 1 to 10 liters / minute. If the spray amount is small, it is difficult to obtain the effect of the present invention. On the other hand, if the spray amount is too large, the processing liquid tends to deteriorate, which is not preferable. The outlet of the circulated processing solution is 1 to 4 mm immediately, and the direction perpendicular to the photosensitive layer of the photosensitive material is 10 to 1 per tank.
It is preferably provided at 00 locations, more preferably 5 to 50 blowing holes per tank. Further, the distance between the blowing hole and the surface of the photosensitive layer is preferably 1.0 to 50 mm, more preferably 2.0 to 20 mm. Further, the flow rate from one blow hole is preferably 1 to 100 cm / sec or more,
More preferably, it is 5 to 50 cm / sec.

In the present invention, the means for spraying the circulating liquid as described above may be provided in any of the processing steps, but is preferably provided at least in the developing step. It is more preferably provided in the steps, and the aspect provided in all the steps is most preferable because the effect of improving the stain of the present invention can be obtained. Further, as a preferred embodiment in which the spraying means is provided in the washing and / or stabilizing step, the washing and / or stabilizing step is divided into at least three or more tanks, and at least the final tank is provided with a circulating liquid spraying means. It is preferably provided in the last tank and the preceding tank, and most preferably provided in all tanks for washing and / or stabilizing. Further, the washing and / or stabilizing step is preferably divided into 3 to 12 tanks, and 5 to 10 tanks are preferable.
More preferably, it is divided into tanks. In addition, it is preferable that the photosensitive material is conveyed between the divided washing and / or stabilizing tanks by moving in a liquid via a blade provided on a wall of the tank from the viewpoint of shortening the aerial time. The nozzle for spraying the liquid is preferably provided between the transport roller and the blade between the tanks. At this time, the spray nozzle may be provided only on the photosensitive layer side of the photosensitive material. However, in a multi-chamber washing step or the like, a method of spraying from both sides of the photosensitive material is preferable because troubles such as jamming during transport hardly occur.

[Compound represented by the general formula [A]]
The compound represented by the general formula [A] used in at least one processing step of desilvering, washing with water and / or stabilizing in the image forming method of the present invention will be described.
In the general formula [A], the alkyl group and aralkyl group represented by R ¹ and R ² have 1 to 8 carbon atoms, and specific examples include a methyl group, an ethyl group, an isopropyl group, and an n- Butyl, cyclopropyl, cyclopentyl, benzyl and the like.

In the general formula [A], each group represented by R ¹ and R ² may be substituted. Preferred substituents include the following. Halogen atom (for example, fluorine atom, chlorine atom, bromine atom), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), aryloxy group (for example, phenoxy group), acylamino group (for example, acetylamino group), Ureido group (for example, unsubstituted ureido group, N-methylureido group), urethane group (for example, methoxycarbonylamino group), sulfonylamino group (for example, methylsulfonylamino group,
Phenylsulfonylamino group), sulfamoyl group (eg, unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl group, N-phenylsulfamoyl group), carbamoyl group (eg, unsubstituted carbamoyl group, N, N-
Diethylcarbamoyl group), sulfonyl group (eg, tosyl group), sulfinyl group (eg, methylsulfinyl group, phenylsulfinyl group), alkyloxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group), acyl group (eg, acetyl group) Group, formyl group, pivaloyl group), acyloxy group (eg, acetoxy group), alkylthio group (eg, methylthio group,
Ethylthio group), arylthio group (for example, phenylthio group), cyano group, sulfo group, carboxy group, hydroxy group, phosphono group, nitro group, sulfino group, phosphonio group and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different. Preferred among these substituents are an alkoxy group, a ureido group, a sulfonylamino group,
Examples include a sulfamoyl group, a carbamoyl group, and a hydroxy group.

The compound of the formula [A] of the present invention may form a salt. Specific examples include sulfates, carbonates,
And hydrochloride. In the general formula [A], preferably, R ¹ represents a hydrogen atom, and R ² represents an alkyl group having 3 to 8 carbon atoms. In the general formula [A], more preferably, R ² has 4 carbon atoms.
Represents an alkyl group of 1 to 6. Hereinafter, the general formula [A] of the present invention will be described.
Specific examples of the compound represented by are shown below, but the compound of the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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The compound represented by the general formula [A] can be synthesized by a known method. For the synthesis of guanidines, see Method der Organishe.
It can be synthesized with reference to nChemie (Houben-Weyl) 4th edition, Vol. 8 (1952), pp. 180-195, and E4 (1983), pp. 608-624. A typical synthesis example is shown. [Synthesis Example 1] (Synthesis method of compound A-1) S-methylisothiourea sulfate 13.9 g (0.05
mol) was suspended in 25 ml of water, and 4.0 g (0.055 mol) of n-butylamine was added under a nitrogen stream.
After heating at 60 ° C. for 5 hours, the mixture was cooled on ice, and the precipitated crystals were collected by filtration. The obtained crude crystals were recrystallized from 20 ml of water to obtain 5.9 g of the desired product (yield: 71.8%). Melting point 212-2
13 ° C. The obtained compound was confirmed to be the target compound by NMR spectrum, IR spectrum and elemental analysis. [Synthesis Example 2] (Synthesis method of compound A-15) S-methylisothiourea sulfate 13.9 g (0.05
mol) was suspended in 25 ml of water, and 4.7 g (0.055 mol) of cyclopentylamine was added under a nitrogen stream. After heating at 60 ° C. for 5 hours, 100 ml of isopropyl alcohol was added, the mixture was cooled to room temperature, and the precipitate was collected by filtration. The obtained crude crystals were combined with 10 ml of water-50 ethanol.
Recrystallized with a mixed solution of 6.6 ml to obtain 6.6 g of the desired product (yield 74.
6%). Melting point 250 ° C or higher. The obtained compound was confirmed to be the desired product by NMR spectrum, IR spectrum and elemental analysis.

Each bath of the active substance removal accelerator of the present invention,
The amount added in the desilvering and washing and / or stabilizing treatment steps is 10 to 10 with respect to the bath in the step of performing the desilvering treatment.
A range of 100 mmol / L is preferred. 10 mmol /
If it is less than L, it is difficult to obtain the effect of removing the active substance, and 10
When the amount exceeds 0 mmol / L, the sharpness of the image after the moist heat storage is deteriorated, and the problem of the stability of the replenisher tends to occur. 5-6 for the bath in the step of washing and / or stabilization.
A range of 0 mmol / L is preferred. If the amount is less than 5 mmol / L or exceeds 60 mmol / L, the same problem as above tends to occur. In the present invention, the desilvering step includes an embodiment in which the bleaching step and the fixing step are separately performed in addition to the so-called bleach-fixing step. In the present invention, the main agent removal accelerator can be added to any of the desilvering step and the washing and / or stabilization step. It is preferable for preventing stain after storage under wet heat.

In the present invention, the desilvering step, washing with water and / or
Alternatively, the compound of the general formula [A] used in any one of the stabilization steps may be used together with a bleaching agent or a fixing agent used in the desilvering step, or various additives used in the washing and / or stabilization step. It can be solidified together with the agent to form a solid processing agent such as powder, granules, tablets and the like. For tableting, it is preferable to adopt a method of granulating the powder and then tableting. Details of the solidification method are shown in column 23, line 25 to column 25, line 3 of JP-A-8-137055.

Next, among the cyan couplers used in the silver halide color photographic light-sensitive material of the present invention, the cyan coupler represented by the above formula (I) will be described. Known cyan couplers other than those represented by the general formula (I) can be used without particular limitation. Here, the Hammett's substituent constant [sigma] p value used in this specification will be briefly described. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constant determined by Hammett's rule is σ
There are p-values and σm values, and these values can be found in many common books, for example, JADean, “Lang
e's Handbook of Chemistry, 12th edition, 1979 (Mc Graw-Hill)
See pages 6-103, 1979 (Nankodo). In addition,
In the present invention, each substituent is limited or described by Hammett's substituent constant σp. Needless to say, even if the value is unknown in the literature, it also includes a substituent that will be included in the range when measured based on the Hammett rule. Although the compound represented by the general formula (I) of the present invention is not a benzene derivative, the σp value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense in the future. The term “lipophilic” as used in the present invention means that the solubility in water at room temperature is 1%.
It is less than 0%.

In the present specification, the term "aliphatic" means a straight-chain, branched or cyclic saturated or unsaturated group, for example, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl. May further have a substituent. Also, aromatic represents aryl,
This may further have a substituent, and a heterocyclic ring (heterocycle) is one having a hetero atom in the ring, including an aromatic group, and further having a substituent. I don't care. The substituents in the present specification and the substituents which may be present on these aliphatic, aromatic, and heterocyclic rings may be any groups that can be substituted unless otherwise specified, and include, for example, an aliphatic group and an aromatic group. Group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic Carbamoyl group, aromatic carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic flufamoyl group, aromatic sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, aliphatic amino group, aromatic amino group, Aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, mercapto group, hydroxy group, cyano group, nitro Group, hydroxyamino group,
Examples include a halogen atom.

Hereinafter, the cyan coupler represented by formula (I) of the present invention will be described in detail. Z ^a and Z ^b represent -C (R ⁵⁾ = or -N =, respectively. However, either one of Z ^a and Z ^b are -N =, the other is -C (R ⁵⁾ =
It is.

R ⁵ represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group. Group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
Examples include a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These groups may be further substituted with substituents as exemplified for R ⁵ .

More specifically, R ⁵ hydrogen atom, halogen atom (for example, chlorine atom, bromine atom), alkyl group (for example, linear or branched alkyl group having 1 to 32 carbon atoms, aralkyl group, alkenyl group, An alkynyl group, a cycloalkyl group or a cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy,
2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamido, tetradecanamido, 2- (2,4
-Di-t-amylphenoxy) butanamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy didecaneamide), an alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5
-Dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2- (3-t-butyl-4)
-Hydroxyphenoxy) dodecaneamide {anilino), a ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl) -N-decylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio,
3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example,
Phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonyl) Amino), a sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4
-Di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy- 4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryl An oxycarbonylamino group (for example, phenoxycarbonylamino), an imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2, 4 Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphospho) Nyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), and an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl).

R ⁵ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. , Sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group Can be mentioned.

More preferably, they are an alkyl group or an aryl group, more preferably, from the viewpoint of cohesion, an alkyl group or an aryl group having at least one substituent, and further preferably, at least one alkyl group or an alkoxy group , A sulfonyl group, a sulfamoyl group, a carbamoyl group, an acylamide group or an alkyl group or an aryl group having a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one alkyl group, acylamide group or sulfonamide group as a substituent. When these substituents are present in the aryl group, it is more preferable to have them at least in the ortho or para position.

[0071] Cyan couplers of the present invention, R ³ and also R ⁴ are both 0.20 or more electron-withdrawing group, and R ³
The sum of the σp values of R ⁴ is one which colored cyan image by 0.65 or more. The sum of the σp values of R ³ and R ⁴ is preferably 0.70 or more, and the upper limit is about 2.0.

R ³ and R ⁴ are Hammett's substituent constant σp
An electron-withdrawing group having a value of 0.20 or more. Preferably,
It is an electron-withdrawing group of 0.30 or more. The upper limit is 1.
It is an electron-withdrawing group of 0 or less.

Specific examples of R ³ and R ^{4 having} an σp value of 0.20 or more include acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro and nitro groups. Group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, Halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, heterocycle Group, halogen atom, azo group, or A selenocyanate group. Among these substituents, the group which can further have a substituent may further have a substituent as described for R ⁵ .

R ³ and R ⁴ are described in more detail.
Examples of the electron-withdrawing group having a value of 0.20 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl) , N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-
(4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-
Butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (E.g., diphenylphosphono), diarylphosphinyl group (e.g., diphenylphosphinyl), alkylsulfinyl group (e.g., 3-phenoxypropylsulfinyl), arylsulfinyl group (e.g.,
3-pentadecylphenylsulfinyl), alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio Groups (eg, acetylthio, benzoylthio), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-
(2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), alkyl halide Groups (eg, trifluoromethane, heptafluoropropane), halogenated alkoxy groups (eg, trifluoromethyloxy), halogenated aryloxy groups (eg, pentafluorophenyloxy), halogenated alkylamino groups (eg, N, N
-Di- (trifluoromethyl) amino), a halogenated alkylthio group (e.g., difluoromethylthio, 1,1,
2,2-tetrafluoroethylthio), an aryl group substituted with another electron-withdrawing group having a σp of 0.20 or more (eg, 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl) A heterocyclic group (eg, 2-benzoxazolyl, 2-benzothiazolyl,
1-phenyl-2-benzimidazolyl, 5-chloro-
1-tetrazolyl, 1-pyrrolyl), a halogen atom (for example, a chlorine atom or a bromine atom), an azo group (for example, phenylazo) or a selenocyanate group. Among these substituents, a group which may have a further substituent is R ⁵
It may further have a substituent as mentioned in the above.

R ³ and R ⁴ are preferably acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl, arylsulfinyl, Alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group,
A halogenated aryloxy group, two or more σp 0.20
An aryl group substituted with the other electron-withdrawing group and a heterocyclic group can be exemplified. More preferred are an alkoxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group. Most preferred as R ³ is a cyano group. Particularly preferred as R ⁴ is an alkoxycarbonyl group, and most preferred is a branched alkoxycarbonyl group (especially a cycloalkoxycarbonyl group).

X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent, and when the group capable of leaving is specifically described, a halogen atom, an alkoxy group, an aryloxy Group, acyloxy group, alkyl or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, carbamoyloxy group, Examples include a heterocyclic carbonyloxy group, a 5- or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group, and the like. These groups may be further substituted with a group allowed as a substituent of R ⁵ .

More specifically, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methanesulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (e.g., 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl Sulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), acylamino group (for example, dichloroacetylamino, heptafluorobutyrylamino), alkyl or arylsulfonamide group (for example, methanesulfonylamino,
Trifluoromethanesulfonylamino, p-toluenesulfonylamino), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), alkyl,
Aryl or heterocyclic thio groups (e.g. dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, N-ethylcarbamoyl) Oxy, N-ethyl-N-phenylcarbamoyloxy),
Heterocyclic carbonyloxy group (eg, morpholinocarbonyloxy, piperidinocarbonyloxy), 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2
-Dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo) and the like. X is an aldehyde or ketone as a leaving group bonded via a carbon atom.
It may take the form of a bis-type coupler obtained by condensing an equivalent coupler. X may contain a photographically useful group such as a development inhibitor and a development accelerator.

Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, and a nitrogen atom at the coupling active site. A 5- or 6-membered nitrogen-containing heterocyclic group bonded by an atom. More preferred X is a halogen atom, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, and particularly preferred are a carbamoyloxy group and a heterocyclic carbonyloxy group. It is.

In the cyan coupler represented by the general formula (I), the group of R ³ , R ⁴ , R ⁵ or X becomes a divalent group, and binds to a dimer or higher polymer or a polymer chain. To form a homopolymer or a copolymer. A homopolymer or a copolymer bonded to a polymer chain is a typical example of an addition polymer having a cyan coupler residue represented by the general formula (I), homo- or copolymer of an ethylenically unsaturated compound. . In this case, the polymer may contain one or more kinds of cyan coloring repeating units having a cyan coupler residue represented by the general formula (I), and one of the non-coloring ethylene type monomers as a copolymer component. It may be a copolymer containing one or more species. The cyan coloring repeating unit having a cyan coupler residue represented by the general formula (I) is preferably represented by the following general formula (P).

[0080]

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In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -COO-
Or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and L represents -CONH-, -NHCONH-,
-NHCOO-, -NHCO-, -OCONH-, -NH-, -COO
-, - OCO -, - CO -, - O -, - S -, - SO 2 -,
-NHSO ₂ - or -SO ₂ NH - represents a. a, b, and c are 0
Or 1 is indicated. Q represents a cyan coupler residue in which a hydrogen atom has been removed from R ³ , R ⁴ , R ⁵ or X of the compound represented by formula (I). As the polymer, a copolymer of a cyan-color-forming monomer represented by a coupler unit of the general formula (I) and a non-color-forming ethylene-like monomer that does not couple with an oxidation product of an aromatic primary amine developer is preferable.

The non-color-forming ethylene type monomer which does not couple with the oxidation product of the aromatic primary amine developer includes:
Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (eg, methacrylic acid) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, di- Acetone acrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, iso-butyl acrylate, 2
-Ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate,
Ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, eg, vinyl Toluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinylilipyridine and 2- and -4-
Vinyl pyridine and the like.

In particular, acrylates, methacrylates and maleates are preferred. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinylic monomer corresponding to the above general formula (I) is used to form a copolymer having physical properties and / or Alternatively, it can be selected such that the chemical properties, eg, solubility, compatibility with the binder of the photographic colloid composition, eg, gelatin, its flexibility, thermal stability, etc., are favorably affected.

[0085] The silver halide light-sensitive material of the cyan coupler of the present invention, the preferably to be contained in the red-sensitive silver halide emulsion layer, it is preferable to so-called internal type coupler. For this purpose, R ^3, R ^And at least one of R ⁵ and X is a so-called ballast group (preferably having a total carbon number of 1).
0 or more), and more preferably 10 to 50 carbon atoms in total. Particularly, it is preferable that R ⁵ has a ballast group. The cyan coupler represented by the general formula (I) is more preferably a compound having a structure represented by the following general formula (III).

[0086]

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In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom or a substituent. As the substituent, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aryl group is preferable, and more preferable ones are described below. R ¹¹ and R ^{12 each} preferably represent an aliphatic group, for example, a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, alkynyl group or cycloalkenyl group having 1 to 36 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, t-butyl, t
-Represents amyl, t-octyl, tridecyl, cyclopentyl, cyclohexyl. The aliphatic group more preferably has 1 to 12 carbon atoms. R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups described above for R ¹¹ and R ¹² . R ¹³ , R ¹⁴ , R
¹⁵ is particularly preferably a hydrogen atom.

Z is necessary for forming a 5- to 8-membered ring,
Represents a group of non-metallic atoms, and this ring may be substituted, may be a saturated ring or may have an unsaturated bond.
Preferred non-metallic atoms include a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom, and more preferably a carbon atom. Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring,
Cyclooctane ring, cyclohexene ring, piperazine ring,
Oxane ring, thiane ring, these rings may be substituted by a substituent as represented by R ⁵ described above. Preferably the ring formed by Z is a cyclohexane ring which may be substituted, especially preferably, 4-position substituted with a substituent as represented by an alkyl group (the aforementioned R ⁵ having 1 to 24 carbon atoms A cyclohexane ring substituted with

R ⁵ of the [0089] Formula (III) has the same meaning as R ⁵ in the formula (I), in particular preferably an alkyl group or an aryl group, more preferably a substituted aryl group.
From the viewpoint of the number of carbon atoms, the number is preferably 1 to 36 in the case of an alkyl group, and preferably 6 to 36 in the case of an aryl group. Among the aryl groups, those in which the alkoxy group is substituted at the ortho position of the bond position with the coupler mother nucleus are not preferred because the light fastness of the dye derived from the coupler is low. In that respect, the substituent of the aryl group is preferably a substituted or unsubstituted alkyl group, and among them, an unsubstituted alkyl group is most preferred. Particularly, an unsubstituted alkyl group having 1 to 30 carbon atoms is preferable.

X ² represents a hydrogen atom or a substituent. The substituent is X ² -C (=
O) Groups which promote the elimination of the O- group are preferred. X ² is preferably a heterocyclic ring, a substituted or unsubstituted amino group, or an aryl group. The hetero ring is preferably a 5- to 8-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom and having 1 to 36 carbon atoms. More preferably,
A 5- or 6-membered ring bonded by a nitrogen atom, of which a 6-membered ring is particularly preferred. These rings may form a condensed ring with a benzene ring or a hetero ring. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine,
Pyrazolidine, thiazolidine, pyrazoline and the like, preferably, morpholine, piperidine,
Particularly, morpholine is preferred. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents of R ^{5 described} above, and further include a cyano group, an alkoxy group (eg, methoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), a chlorine atom, a hydroxyl group, a carboxyl group, and the like. May be substituted. As the substituted amino group,
Disubstitution is preferred over monosubstitution. As the substituent, an alkyl group is preferable.

The aryl group preferably has 6 to 36 carbon atoms, and more preferably a monocyclic ring. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 4-dichlorophenyl and the like. The general formula (III) used in the present invention
The cyan coupler represented by) has an oil-solubilizing group in the molecule, is easily soluble in high-boiling organic solvents, and is formed by oxidative coupling of the coupler itself and the coupler with a color-forming reducing agent (developer). Preferably, the dye applied is non-diffusible in the hydrophilic colloid layer. In the coupler represented by the general formula (III), R ⁵ contains a coupler residue represented by the general formula (III) to form a dimer or higher multimer, or R ⁵ represents a polymer chain. They may be contained to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is represented by the general formula (II
Typical examples are homopolymers or copolymers of addition polymer ethylenically unsaturated compounds having a coupler residue represented by I). In this case, the polymer may contain one or more types of cyan coloring repeating units having a coupler residue represented by the general formula (III), and an acrylic acid ester, a methacrylic acid ester, or a maleic acid ester as a copolymer component. It may be a copolymer containing one or more non-color-forming ethylenic monomers which do not couple with the oxidation product of an aromatic primary amine developer such as phenol. Specific examples of the cyan coupler defined in the present invention are shown below, but the invention is not limited thereto.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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The compound represented by formula (I) can be prepared by a known method, for example, as described in JP-A-5-150423 and 5-2.
No. 55333, No. 5-202004, No. 7-4837
No. 6 can be synthesized. Hereinafter, specific synthesis examples of the compound represented by the general formula (I) will be shown. Synthesis Example 1 Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following route.

[0106]

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[Synthesis of Compound (b)] 2,6-Di-t-
Butyl-4-methylcyclohexanol, 17 g (75
mmol) in acetonitrile (200 ml) at 0 ° C. in trifluoroacetic anhydride, 10.6 ml (75 mmol).
l) was added dropwise, followed by 15.6 g of compound (a) (6
0.4 mmol) was added slowly. After the reaction solution was stirred at room temperature for 2 hours, 300 ml of water and 300 ml of ethyl acetate were added.
ml was added and extracted. The organic layer was washed with aqueous sodium bicarbonate, water and brine. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized with acetonitrile.
19.6 g of (b) was obtained. [Synthesis of Compound (c)] To a solution of 19.6 g of (b) in 200 ml of ethyl acetate, 5 ml of pyridine was added, and bromine was added dropwise under cooling with water. After stirring for 1 hour, water 300m
l, 300 ml of ethyl acetate was added and extracted. After extraction,
After the ethyl acetate layer was dried over magnesium sulfate, the solvent was distilled off, and acetonitrile was added to the residue, followed by recrystallization. (C)
Was obtained 18.0 g.

[Synthesis of Compound (e)] A solution of 2.2 g of methyl cyanoacetate in 20 ml of dimethylacetamide was added at 0 ° C.
Then, 0.8 g of sodium hydride was slowly added thereto, followed by stirring at room temperature for 30 minutes. (Solution S) Dimethylacetamide 5
10.0 g of (c) dissolved in 0 ml was slowly dropped into (Solution S) under ice cooling. After stirring for 1 hour, 4 g of sodium hydroxide dissolved in 20 ml of water and 20 ml of methanol were added to the reaction solution, and the reaction temperature was maintained at 50 ° C.
Stirred for hours. After the reaction, 200 ml of ethyl acetate was added,
Neutralized with aqueous hydrochloric acid. After washing with water, the ethyl acetate layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude compound (e).

[Synthesis of Exemplified Compound (1)] 8.0 g of the obtained crude compound (e) was added to 40 ml of dimethylacetamide.
It was dissolved in 6 ml of pyridine, and 4.3 g of morpholinocarbamoyl chloride was added at 0 ° C. After stirring at room temperature for 2 hours, the mixture was poured into 200 ml of diluted hydrochloric acid, and ethyl acetate was added.
Extracted with 00 ml. After washing the organic phase with water and drying over magnesium sulfate, the solvent is distilled off under reduced pressure, hexane is added to the residue, and the residue is crystallized to give Exemplified Compound (1).
0 g was obtained. Melting point: 256-257 ° C.

[Synthesis Example 2. Synthesis of Exemplified Compound (25)]
In the synthesis of compound (1), 4.5 g of diallylcarbamoyl chloride was added instead of morpholinocarbamoyl chloride, and the mixture was stirred at room temperature for 2 hours. After the reaction,
The mixture was poured into 200 ml of diluted hydrochloric acid and extracted with 200 ml of ethyl acetate. After the organic phase was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, hexane was added to the residue, and the residue was crystallized to obtain 5.5 g of the desired exemplary compound. Melting point is 2
19 ° C to 220 ° C. Other compounds can be synthesized similarly.

Next, the compound represented by formula (II) of the present invention will be described in detail. In the compound represented by the general formula (II), when R ^a1 or R ^a2 is an alkyl group, the sum of the carbon number including the substituent is preferably in the range of 1 to 30, more preferably 1 to 20. Range.
When R ^a1 or R ^a2 is an aryl group, the total number of carbon atoms including the substituent is preferably 6 to 30. R
^{When a3} or ^Ra4 is an alkyl group, the sum of the carbon atoms including the substituent is preferably in the range of 1 to 24, more preferably 1 to 18. And R ^a3 or R
^{When a4} is an aryl group, the sum of the number of carbon atoms including the substituent is preferably in the range of 6 to 24.

The group which can be substituted with an alkyl group for R ^{a1 to} R ^a4 is not particularly limited, but includes a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a sulfonyl group, and a phosphoryl group. , An alkylthio group, an arylthio group, an acylamino group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a carbamoylamino group, and an alkoxycarbonylamino group are preferable, and in particular, a halogen atom, an alkoxy group,
Acyloxy, alkoxycarbonyl, aryloxy and acylamino groups are more preferred. The group which can be substituted for the alkyl group may contain an unsaturated bond.

In the case where R ^{a1 to} R ^a4 are aryl groups, the substituents may be the same as those of the above-mentioned substituents of the alkyl group. Preferred examples of the group include an alkyl group, a halogen atom and an alkoxy group. Group, acyloxy group and acylamino group.

[0114] In the preferred range of the number range of 6 to 30 carbons of R ^a5, more preferably from 6 to 24. The group that can be substituted for R ^a5 is the same as the group that can be substituted for the aryl group of R ^{a1 to} R ^a4 , and the preferred groups are also the same. The compound of the general formula (II) is used by being fixed in oil droplets and dispersed in a hydrophilic colloid. Therefore, it is necessary to make the compound lipophilic. It is preferable that at least any one lipophilic groups R ^a1 to R ^a5 (oil-solubilizing group) is introduced, the total number of carbon atoms of R ^a1 to R ^a5 is at least 14
It is necessary to be above. The total number of carbon atoms is preferably in the range of 16 to 40, more preferably 18
~ 36.

[0115] Preferred ranges number of carbon atoms of R ^a5 in the range of 6 to 0 and more preferably in the range of 6 to 24. The group that can be substituted for R ^a5 is the same as the group that can be substituted for the aryl group of R ^{a1 to} R ^a4 , and the preferred groups are also the same. General formula (I
The compound (I) is used by being fixed in oil droplets and dispersed in a hydrophilic colloid. Therefore, it is necessary to make the compound lipophilic. Either at least one of R ^a1 to R ^a5
Preferably the lipophilic group (oil-solubilizing group) is introduced into One, the total number of carbon atoms of R ^a1 to R ^a5 is required to be at least 14 or more. The total number of carbon atoms is preferably in the range of 16 to 40, more preferably 18 to 40.
36.

Preferred groups for introducing the oil-solubilizing group are R ^{a1 and} R ^a5 . If oil-solubilizing group is introduced into R ^a1, as the oil-solubilizing group substituted with an unsubstituted linear or branched alkyl group or an alkoxy group, an aryloxy group, an acyl group or an alkoxycarbonyl group having 12 to 24 carbon atoms The alkyl group having 12 to 36 carbon atoms is preferable, and the alkyl group having 14 to 20 carbon atoms is particularly preferable. At this time, ^Ra5
May or may not have a substituent, but is preferably unsubstituted. When an oil-solubilizing group is introduced into ^Ra5 , the oil-solubilizing group is preferably an alkyl group having 12 to 30 carbon atoms, an alkoxy group, an acyloxy group, or an acylamino group, and particularly preferably an alkoxy group having 12 to 24 carbon atoms. R ^a3 and R ^a4 are preferably hydrogen atoms. Among the compounds of the general formula (II), a compound represented by the following general formula (IV) or (V) is preferable from the viewpoint of storage stability.

[0117]

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Next, the compound represented by formula (IV) will be described in detail. R ^a and R ^b each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group having a total of 1 to 30 carbon atoms including the carbon number of the substituent. When R ^a and R ^b are an aryl group, the substituent that substitutes the aryl group is the substituent described in the description of R ^a1 in the formula (II), and specific examples thereof include those described in the description of R ^a1. Can be Among them, more preferred are an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an aminocarbonylamino group, and an alkoxycarbonylamino group. Most preferably, an alkyl group (having 1 to 1 carbon atoms)
0), a halogen atom (a chlorine atom and a bromine atom), and an alkoxy group (1 to 10 carbon atoms). When R ^a and R ^b are aryl groups, unsubstituted aryl groups are more preferable than those having a substituent. When R ^a and R ^b are alkyl groups, the total number of carbon atoms including the number of carbon atoms of the substituent is 1
~ 30. The unsubstituted alkyl group may be linear or branched. As a straight-chain alkyl, it has 1 to 26 carbon atoms.
(Eg, methyl, ethyl, n-propyl, n-butyl,
Those having n-hexyl, n-octyl, n-decyl, n-octadecyl, n-eicosyl) are preferable, and the branched alkyl includes 3 to 26 carbon atoms (for example, i-propyl,
t-butyl, 2-ethylhexyl) are preferred. R ^a ,
When R ^b is a substituted alkyl, the substituent is a group represented by the formula (II):
It is a substituent described in the description of ^a1 , and the total number of carbon atoms including the number of carbon atoms of the substituent is preferably from 1 to 20. Specific examples thereof include those described in the description of ^Ra1 , and specific examples thereof include ethoxymethyl, acetoxymethyl, stearoyloxymethyl, p-phenoxymethyl, 1-
Nitrophenoxymethyl, 1-chlorooctyl and the like.

R ^a3 and R ^a4 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When R ^a3 and R ^a4 are a substituted alkyl group or a substituted aryl group, the substituent is the substituent described in the description of R ^{a1 in} the formula (II), and specific examples thereof are also those described in the description of R ^a1. Is mentioned. When R ^a3 or R ^a4 is an alkyl group, it preferably has 1 to 20 carbon atoms. An unsubstituted alkyl group is preferable to an alkyl group having a substituent. When R ^a3 or R ^a4 is an aryl group, it has 6 carbon atoms.
~ 20 is preferred. Preferably, at least one of R ^{a3 and} R ^a4 is a hydrogen atom, and most preferably,
^Ra3 and ^Ra4 are both hydrogen atoms.

R ^a5 is a substituted or unsubstituted aryl group, and the substituent to be substituted on the aryl group is R ^{a1 of the} formula (II)
Are the substituents described above. Specific examples of the substituent include those described in the description of the formula (II). The substituent is preferably an alkyl group (1 to 20 carbon atoms, for example, methyl,
Ethyl, i-propyl, t-butyl, n-octyl),
An alkoxy group (1 to 20 carbon atoms, for example, methoxy, ethoxy, i-propoxy, t-butoxy, n-octyloxy, n-tetradecyloxy, n-hexadecyloxy, n-octadecyloxy), an acylamino group (carbon number 1-20, for example, acetylamino group, propionylamino, stearoylamino), alkoxycarbonylamino (2-20 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, octyloxycarbonylamino), aminocarbonylamino (1-2 carbon atoms)
0, for example, dimethylaminocarbonylamino, dioctylaminocarbonylamino), alkylsulfonylamino group (1 to 20 carbon atoms, for example, methanesulfonylamino, ethanesulfonylamino, butanesulfonylamino, octanesulfonylamino), and arylsulfonylamino (C6) -20, for example, benzenesulfonylamino, toluenesulfonylamino, dodecylbenzenesulfonylamino).

The compound of the formula (IV) has a structure represented by R
It is preferred that at least one of ^a , R ^b , R ^a3 , R ^a4 , and R ^a5 has a so-called ballast group. Molecular weight 2
00 or more, more preferably 250 or more, and 30 or more.
0 or more is more preferable, and 350 or more is most preferable. The compound of the formula (V) will be described in detail. R in formula (V)
^a3 , R ^a4 and R ^a5 have the same ^{meanings as} in formula (IV). The same applies to specific examples and preferable examples. R ^c represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. When R ^c is an alkyl group or an aryl group, the substituent is the substituent described in the description of R ^{a1 in} the formula (II). Specific examples thereof include those described in the description of ^Ra1 . R ^c is preferably an alkyl group (1 to 20 carbon atoms, for example, methyl, ethyl, i-propyl,
t-butyl, n-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, i-octadecyl, 2-ethylhexyl, 2-methoxyethyl, 2-chloroethyl), an aryl group (C6-20, for example, phenyl,
Naphthyl, p-chlorophenyl, m-methoxyphenyl, o-methylphenyl).

The compound of the formula (V) has a structure represented by R
It is preferable that at least one of ^c , R ^a3 , R ^a4 , and R ^a5 has a so-called ballast group. The molecular weight is preferably 200 or more, more preferably 250 or more, still more preferably 300 or more, and most preferably 350 or more. Among the phenidone compounds represented by the general formulas (IV) and (V) of the present invention,
When added to the non-photosensitive layer, more preferred are compounds represented by the general formula (IV). When added to the photosensitive layer, the compound represented by formula (V) is more preferable. Among the compounds represented by the general formula (V), R ^c is an alkyl group, R ^a3 and R ^a4 are both hydrogen atoms,
Preferably, R ^a5 is a substituted or unsubstituted aryl group. Among them, whether the aryl group of R ^a5 is unsubstituted,
Alternatively, the substituent is preferably an alkoxy group, an acylamino group, an alkylsulfonylamino group, or an arylsulfonylamino group, and more preferably unsubstituted or substituted with an alkoxy group. As R ^c , an unsubstituted alkyl group is more preferable than an alkyl group having a substituent. Most preferred of the compound represented by the general formula (V) is that R ^c is an unsubstituted alkyl group, R ^a3 and R ^a4 are hydrogen atoms,
R ^a5 is an unsubstituted aryl group. Specific examples of the compound represented by formula (IV) or (V) of the present invention are shown below, but it should not be construed that the invention is limited thereto.

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[0128]

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[0131]

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A method for synthesizing the compounds represented by formulas (IV) and (V) will be described. The compound represented by the general formula (IV) of the present invention can be synthesized according to the following synthesis method.

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Compound (V) -A and hydrazine are condensed to synthesize a compound represented by formula (V). Compound (V) in -A, R ^d is an alkyl group or an aryl ^{group, R c, R a3, R} a4 and R ^c in formula (IV), R ^a3, R
Synonymous with ^a4 . R ^a5 of hydrazine is R of general formula (V)
Synonymous with ^a5 . In this reaction, it is preferable to cause one or more equivalents of a base to act in a suitable solvent. When a hydrazine salt is used, it is preferable to use two or more equivalents of a base to release hydrazine. The base is preferably an alkoxide, and examples thereof include potassium tert-butoxide and sodium methoxide. Examples of the solvent include n-butanol, t-butanol, dimethylsulfoxide, dimethylacetamide and the like. The reaction temperature can be generally from -20 ° C to 180 ° C, preferably from 0 ° C to 120 ° C, and more preferably from 30 ° C to 90 ° C. Reaction times are generally from 5 minutes to 24
The time is appropriate, but preferably 30 minutes to 6 hours, more preferably 1 hour to 3 hours. The molar ratio of hydrazine to compound (V) -A is preferably 2: 1 to 1: 2. More preferably, 1.
2: 1-1: 1.2.

The compound represented by the general formula (IV) is synthesized by reacting the general formula (IV) -A with hydrazine. In the general formula ^{(IV) -A, R a,} R b, R a3, R a4 is an R ^a of the general formula (IV), and R ^b, R ^a3, R ^a4 synonymous. L ¹ ,
L ² is a group that leaves in a nucleophilic reaction. L ¹ is preferably a halogen atom or an oxygen atom activated by a condensing agent. L ² is preferably a hydroxy group,
It is a halogen atom. The reaction temperature is generally -20 ° C to 18
Although it can be performed at 0 ° C., it is preferably 0 ° C. to 120 ° C., and more preferably 30 ° C. to 90 ° C. The reaction time is generally from 5 minutes to 24 hours, but is preferably from 1 hour to 6 hours. In the reaction of compounds (IV) -B to (IV), acidic conditions are preferred when L ² is a hydroxyl group. When L ² is a halogen atom, the reaction may be performed under any of neutral, acidic and alkaline conditions.

Synthesis of Compound (52) Exemplified Compound 52 was synthesized by the following route.

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(1) First Step 256 g (1.94 mol) of methyl succinate and 800 ml of methanol were stirred at room temperature, and 375 g (1.94 mol) of sodium methylate (28% by weight) was added dropwise thereto. Then, 592 g of 1-bromohexadecane
(1.94 mol) was added dropwise. After refluxing for 3 hours, methanol was distilled off, and the reaction solution was poured into 1N aqueous hydrochloric acid. After extraction with hexane, washing with brine and drying, the solvent was distilled off to obtain 511 g (1.43 mol) of an intermediate a (yield: 73.7).
%).

(2) Second step Intermediate A 511 g (1.43 mol) and methanol 8
A solution prepared by dissolving 94.6 g (1.43 mol) of potassium hydroxide (85%) in 800 ml of methanol was added dropwise to 00 ml of the solution with stirring at 35 ° C. After reacting at 40 ° C. for 2 hours, a solution obtained by dissolving 130 ml of concentrated hydrochloric acid in 500 ml of water was further added dropwise. The precipitated crystals are collected by filtration, and water and n
-Washing with hexane gave Intermediate b. The intermediate b was used in the next step without drying.

(3) Third Step Intermediate B (total amount: 1.43 mol) and methanol 1.0
Of dimethylamine and stirring at 20 ° C.
15 g (1.57 mol) were added dropwise. Then 3 more
135 g (1.57 mol) of a 5% aqueous folimarin solution was added dropwise and reacted at 20 ° C. for 24 hours. The precipitated crystals were collected by filtration, washed with water and methanol, and then dried to obtain 396 g (1.28 mol) of intermediate C (yield: 89.5).
%).

(4) Fourth step 145 g (1.34 mol) of phenylhydrazine and 1.5 l of toluene were stirred at 140 ° C., and the solvent was distilled off using a Dean-Stark dehydrator until the internal temperature reached 100 ° C. . Subsequently, sodium methylate (28% by weight)
After dropping 272 g (1.41 mol) of methanol and distilling off methanol, a solution of 396 g (1.28 mol) of the intermediate c in 400 ml of toluene was dropped. After refluxing for 30 minutes,
After cooling on ice, 150 ml of concentrated hydrochloric acid was added.
0 ml was added. The insoluble matter was removed by filtration, and the solution was cooled. After the precipitated crystals were collected by filtration, washed with water and n-hexane, and dried, 393 g of compound (51) (1.02
mol) was obtained (yield 79.7%). Other compounds can be synthesized similarly.

The effect of using the compound represented by the general formula (II) of the present invention is as follows: when a highly active cyan coupler having a pKa of 8.7 or less is used, cyan fog, cyan stain, and treated color mixture are remarkably observed. And the like, without significantly affecting other photographic performance, and is an effect commonly seen in combination with a cyan coupler having a pKa of 8.7 or less. The cyan coupler of the present invention represented by the general formula (I) has a feature that the pKa is low due to its structure, and the use of the compound of the general formula (II) is particularly effective. The effect is particularly large when the pKa of the above-mentioned cyan coupler is 8.0 or less, and a greater effect is seen when the pKa is 7.5 or less, which is particularly preferable. The pKa of the coupler was determined by the pH titration curve in a THF / water = 6/4 mixed solvent system.
Can be easily measured. The compound represented by the general formula (II) of the present invention can be used together with a cyan coupler in a cyan coloring layer. In this case, it is more preferable that the compound of the general formula (II) has a structure represented by the general formula (V), since the effect is larger and the influence of a decrease in color development is small. The compound of the general formula (II) can also be used for a non-photosensitive colloid layer. In this case, it is desirable to use in combination with a known color mixing inhibitor such as hydroquinones. When used in a non-photosensitive layer, the compound of the general formula (II) is more preferably a compound of the structure represented by the general formula (IV) from the viewpoint of its effect. Furthermore, in the present invention, the compound of the above (II) may be used in at least one of the cyan coloring layer and at least one of the non-color-forming hydrophilic colloid layers.
It can also be added to both layers.

The preferred coating amount of the cyan coupler of the present invention depends on the molar extinction coefficient of the cyan coupler.
In the range of 01~1g / m ^2, preferably 0.05 to 0.
5 g / m ² . When the cyan coupler to be used is a coupler represented by the general formula (II), the preferred amount is in the range of 0.01 to 0.6 g / m ² , more preferably 0.05 to 0.4 g / m ^2. m ² , more preferably 0.1
０．３0.3 g / m ² . The ratio of the amount of the cyan coupler to the amount of the silver halide used depends on the equivalentity of the coupler, and the 2-equivalent coupler has an Ag / coupler ratio of 1.5 to 8,4.
For equivalent couplers, the range is 3-16. In the present invention, 2-equivalent couplers having a low pKa are preferred, in which case the Ag / coupler ratio is in the range 1.5-8, preferably 2-5.
6, more preferably in the range of 2.5-5.

In the present invention, general formulas (II), (IV),
Or the compound represented by (V) is a non-photosensitive hydrophilic colloid layer containing a high-boiling organic solvent, a color mixture inhibitor, an ultraviolet absorber,
Alternatively, it can be used by dispersing it together with an organic compound such as a polymer dispersant and a dispersing aid such as a surfactant. The amount used is in the range of 0.1 mol% to 200 mol%, preferably 1 mol%, based on the cyan coupler to be coated.
-100 mol%, more preferably 5-50 mol%. It is preferable that the compound represented by formula (II), (IV) or (V) of the present invention is used simultaneously in a cyan coloring layer in addition to the non-photosensitive colloid layer. In this case, the amount used in the cyan coloring layer is 1 to 100 with respect to the cyan coupler.
It is preferably in the range of 5 mol% to 50 mol%. The compound of the general formula (II), (IV) or (V) can be preferably used in combination with the layers other than those described above, but in this case, the total amount used is 1 to 1 with respect to the cyan coupler.
It is in the range of 200 mol%, more preferably 5 to 100 mol%, and still more preferably 10 to 50 mol%.

The cyan couplers of the present invention may be, in addition to the above-mentioned compounds, compounds represented by the following formulas (VI), (VII), (VIII) and (IX) in terms of hue adjustment and promotion of color formation. It is preferred to use one of the following. These compounds can be used in combination of several types depending on the purpose.

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In the general formula (VI), the substituent R ^s is an alkyl group,
Represents an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. The substituent R ^s is preferably an alkoxy group or an alkoxycarbonyl group, and most preferably an alkoxy group. The substitution position of the substituent R ^s may be ortho, meta or para to the COOH group, but is preferably ortho to the hue adjusting ability. The benzene ring may further have a substituent such as a halogen atom or an alkyl group.

In the general formula (VII), the substituent R ^t represents an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group. These substituents further include a halogen atom,
It may have a substituent such as a hydroxyl group, an alkyl group, an aryl group, an alkoxy group and an ester group. The substituent R ^t is preferably an alkoxy group or an alkoxycarbonyl group, and most preferably an alkoxy group. Ortho substitution position CONH ₂ group substituents R ^t, meta,
Although any of them may be used, it is preferably in the ortho position in terms of hue adjusting ability. The benzene ring may further have a substituent such as a halogen atom or an alkyl group.

In the general formula (VIII), the substituents R ^u , R ^v , R ^w
And R ^x may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group or an acyl group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. Substituents R ^u, R ^v, preferably as R ^w and R ^x is a hydrogen atom, an alkyl group or an aryl group, an alkyl group or a cycloalkyl group is more preferably a cycloalkyl group branch is most preferred. The substitution position of the two carbamoyl groups may be any of ortho, meta and para-, but it is particularly preferred that the carbamoyl group is meta at the point of hue adjusting ability. The benzene ring may further have a substituent such as a halogen atom or an alkyl group.

In the general formula (IX), the substituent Q represents a> N—R ^y group or a> C (R ^y1 ) R ^y2 group. The substituents R ^y , R ^y1 and R ^y2 each represent a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxycarbonyl group or an acyl group. Also,
The substituent R ^z represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or an acyloxy group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. The substituent R ^y is preferably an alkyl group or an aryl group, and more preferably an alkyl group substituted with a linear or branched alkyl group or an aryl group. The substituent R ^z is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group.
R ^y1 and R ^y2 are preferably a hydrogen atom or an alkyl group.

The following formulas (VI), (VII) and (VII)
Specific examples of the compounds represented by I) and (IX) are given below.
The compounds used in the present invention are not limited to the following.

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[0154]

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In order to introduce the cyan coupler and the like into the silver halide light-sensitive material, known dispersion methods such as an oil-in-water dispersion method and a latex dispersion method using a high-boiling organic solvent described later can be used. In the oil-in-water dispersion method, a cyan coupler or other photographically useful compound is dissolved in a high-boiling organic solvent, and the dispersion is dispersed in a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a dispersing agent such as a surfactant, using an ultrasonic, colloid mill. It can be emulsified and dispersed into fine particles by a known device such as a homogenizer, a Menton-Gaulin, a high-speed dissolver, or the like. In dissolving the coupler, an auxiliary solvent can be further used. The auxiliary solvent referred to here is an organic solvent effective at the time of emulsification and dispersion, and refers to one that is substantially removed from the photosensitive material after the drying step at the time of coating, for example, ethyl acetate, acetate of a lower alcohol such as butyl acetate, Examples include ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, methyl carbitol propionate, and cyclohexanone.

Further, if necessary, an organic solvent which is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide and the like can be partially used in combination. These organic solvents can be used in combination of two or more kinds. Further, from the viewpoint of improving the aging stability during storage in the emulsified dispersion state, suppressing photographic performance changes and improving the aging stability of the final composition for coating mixed with the emulsion, the emulsified dispersion may be depressurized as necessary. All or a part of the auxiliary solvent can be removed by a method such as distillation, noodle washing or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably from 0.04 to 0.50 μm, more preferably from 0.05 to 0.30 μm, and most preferably from 0.08 to 0.20 μm. It is. The average particle size was measured using the Coulter Submicron Particle Analyzer mode.
It can be measured using 1N4 (Coulter Electronics) or the like.

In the oil-in-water dispersion method using a high-boiling organic solvent, the weight ratio of the high-boiling organic solvent to the total weight of the cyan coupler used can be arbitrarily determined, but is preferably 0.1.
Or more, and 10.0 or less, more preferably 0.3 or more and 7.0 or less, and most preferably 0.5 or more and 5.0 or less. It is also possible to use a high boiling point organic solvent without using it at all.

With respect to the cyan coupler of the present invention, the conventionally used 2-acylamino-5-alkylphenol-type cyan coupler, 2,5-diacylaminophenol-type cyan coupler and 2-carbamoyl-1-
A naphthol type cyan coupler can be used in combination.
Among them, a combination with a 2-acylamino-5-alkylphenol-type cyan coupler is particularly preferable. In this case, the cyan coupler to be used in combination is 1 to the coupler of the present invention.
It is in the range of 50 mol%, preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

In order to improve the image fastness of the cyan coupler of the present invention, a method of co-dispersing a polymer insoluble in water with an organic solvent in oil droplets is also preferably used. In this case, the polymer is preferably a styrene, acrylamide, methacrylamide, acrylate, methacrylate-based polymer or a copolymer thereof, and the number average molecular weight is preferably in the range of 20,000 to 200,000. In order to improve the stability of the emulsion, an oligomer molecule having a molecular weight of about 500 to 5,000 is preferably used, and a styrene oligomer, an α-methylstyrene oligomer and the like are preferable. In particular, styrene and α-
Methylstyrene oligomers are particularly preferred in terms of solubility. It is also preferable to add an amphiphilic polymer to the coating solution to promote color formation. In this case, a copolymer of acrylic acid or methacrylic acid and these esters is more preferred. Particularly, a copolymer of methacrylic acid and butyl acrylate is a particularly preferable compound having a large effect.

The color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing, and it is preferable to use various precursors of the color developing agent for the purpose. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597;
No. 9, RD Magazine No. No. 14850 and Id. 1515
No. 9, the Schiff base type compound; 13924
No. 3,719,4.
No. 92 metal salt complexes and urethane compounds described in JP-A-53-135628. The color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones as needed for the purpose of accelerating color development. A typical compound is described in JP-A-56-643.
No. 39, No. 57-144547, and No. 58-115
438 etc.

The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., and among them, a color photographic paper is preferable.
As the photographic support used in the present invention, a transmission type support or a reflection type support can be used. As the transmission type support, a transmission film such as a cellulose triacetate film or polyethylene terephthalate,
A material in which an information recording layer such as a magnetic layer is provided on a polyester of 6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
Pyrazoline-based fluorescent whitening agents can be used, and more preferred are benzoxazolylnaphthalene-based and benzoxazolylstilbene-based fluorescent whitening agents. Specific examples of the fluorescent whitening agent contained in the water-resistant resin layer include, for example, 4,4 ′
-Bis (benzoxazolyl) stilbene and 4,4'-
Bis (5-methylbenzoxazolyl) stilbene and a mixture thereof are exemplified. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

As the silver halide emulsion for use in the present invention, silver chloro (iodide), silver chloro (iodo) bromide, silver (iodo) bromide emulsion and the like can be used. A silver chloride or silver chlorobromide emulsion having a silver content of 95 mol% or more is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is preferable. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

The above-mentioned reflection type support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

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[Table 2]

The cyan, magenta and yellow couplers used in the present invention are described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Lines 6 to 35, lower right column, line 11 and EP 0355, 660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eyes, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signals of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. When the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, a preferable exposure time is 10-4 seconds or less, more preferably 10-6 seconds or less.

The preferred scanning exposure method applicable to the present invention is described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

As the method of developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developing solution containing an alkali agent and a developing agent, and a developing solution containing a developing agent in the photosensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-2343.
No. 88, Japanese Patent Application No. 7-334190, 7-33419
The hydrazine-type compounds described in Nos. 2, 7-334197, and 7-344396 are preferable.

Further, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator solution containing hydrogen peroxide described in Japanese Patent Application No. 297354/1997 and Japanese Patent Application No. 7-334202 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
-234388 can be used.

[0179]

EXAMPLE 1 After a corona discharge treatment was applied to the surface of a support having both sides of a paper covered with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. To a seventh layer were sequentially coated to prepare a sample (000) of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.

[Silver halide photographic light-sensitive material (photographic paper)
Preparation of (000)] Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-9) 1
0 g, color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cpd-12) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 ml of ethyl acetate, and this solution was emulsified and dispersed in 6500 g of a 10% aqueous gelatin solution containing 200 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion C.

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On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C having a size of 0.41 μm (silver molar ratio). The coefficients of variation are 0.09 and 0.11, respectively.
In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain).
This emulsion contains red-sensitive sensitizing dyes G and H shown below,
5. For large size emulsion C per mole of silver, respectively.
0 × 10 ^-5 mol and 9.0 × 10 ^-5 mol for small-size emulsion C were added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

[0184]

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The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0186]

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The following were used as the silver chlorobromide emulsion and the spectral sensitizing dye in each photosensitive emulsion layer. <Blue-sensitive emulsion layer> Silver chlorobromide emulsion A: cubic, average grain size 0.72 μm
3: 7 mixture of large size emulsion A of formula (1) and small size emulsion A of 0.60 μm (silver molar ratio). The coefficient of variation of the particle size distribution was 0.08 and 0.10. In each size emulsion, 0.3 mol% of silver bromide was contained locally on a part of the surface of the grain having silver chloride as a substrate.

Sensitizing dyes A, B and C are silver halide 1
Per mole, 1.4 × 1 for large emulsions
^0-4 moles, 1.7 × 1 each for small size emulsions
^0-4 moles were added.

[0189]

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<Green-sensitive emulsion layer> Silver chlorobromide emulsion B: cubic, average grain size 0.45 μm
1: 3 mixture of large size emulsion B and small size emulsion B of 0.35 μm (silver molar ratio). The variation coefficients of the particle size distribution are 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain. Sensitizing dye D was used in an amount of 3.0 × 10 ^-4 mol for a large-sized emulsion, 3.6 × 10 ^-4 mol for a small-sized emulsion, and sensitizing dye E per mol of silver halide. Per mol of silver halide, 4.0 × 10 ^-5 mol for large-size emulsion and 7.0 for small-size emulsion.
× 10 ⁻⁵ mol, and 2.0 × 10 ⁻⁴ mol of sensitizing dye F per mol of silver halide for a large-size emulsion.
2.8 × 10 ^-4 mol was added to the small size emulsion.

[0191]

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<Red-sensitive emulsion layer> Silver chlorobromide emulsion C: cubic, average grain size 0.50 μm
1: 4 mixture (large silver emulsion) of large size emulsion C and small size emulsion C of 0.41 μm. The variation coefficients of the particle size distribution are 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain. Sensitizing dyes G and H were added to a large emulsion at 6.0 × / mol silver halide, respectively.
^10-5 mol, 9.0 × each for small size emulsions
10 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

[0193]

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Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 3 per mol of silver halide. ^-4 mol, 1.0 × 10 ^-3
Mol and 5.9 × 10 ^-4 mol. Further, the second layer (color mixture preventing layer), the fourth layer (color mixture preventing layer), the sixth layer (ultraviolet ray absorbing layer) and the seventh layer (protective layer) are also 0.2 mg / m ² and 0.2 mg respectively. / M ² , 0.6 mg / m
² and 0.1 mg / m ² . Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol per mol of silver halide, respectively. 2 × 10 ^-4 mol was added. In the red-sensitive emulsion layer, a copolymer of methacrylic acid and butyl acrylate (weight ratio 1: 1) was used.
1, average molecular weight 200,000 to 400,000) to 0.0
5 g / m ² were added. Further, disodium catechol-3,5-disulfonate was added to the second, fourth and sixth layers at 6 mg / m ² , 6 mg / m ² and 18 mg / m ² respectively.
² was added. To prevent irradiation, the following dyes were added to each emulsion layer (the amount in parentheses indicates the coating amount).

[0195]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [white pigment (TiO ₂ ; content of 16% by weight, Zn
O; content of 4% by weight) and 8/2 of a fluorescent brightener (4,4'-bis (benzoxazolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl) stilbene.
Mixture: 0.05% by weight), including blue dye (ultramarine)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.23

[0197]

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Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

[0199]

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Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-1) 0.05 Ultraviolet absorber (UV- 2) 0.03 UV absorber (UV-3) 0.02 UV absorber (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 colors Image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

[0201]

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[0202]

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Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C 0.20 Gelatin 1.11 Cyan coupler (ExC-1) 0.30 Ultraviolet absorber (UV-1) 0.14 Ultraviolet absorber ( UV-2) 0.05 UV absorber (UV-3) 0.04 UV absorber (UV-4) 0.06 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol (Modified) Degree 17%) 0.04 liquid paraffin 0.02 surfactant (Cpd-13) 0.01

[0206]

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[Silver halide photographic light-sensitive material (photographic paper)
Production of (001)] In the production of photographic paper (000),
A silver chlorobromide emulsion of a red-sensitive emulsion of the fifth layer, a cyan coupler,
Photographic paper (001) was produced in the same manner except that the following were used as the color image stabilizer and the solvent. Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion D: cubic, large-size emulsion C having an average grain size of 0.50 μm and 0. 1: 4 mixture with small size emulsion C of 41 μm (silver molar ratio). The coefficient of variation of the particle size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain. 0.12 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd-6) 05 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 colors Image stabilizer (Cpd-15) 0.06 Color image stabilizer (Cpd-16) 0.09 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0.01 Solvent (Solv) -5) 0.15 Solvent (Solv-8) 0.05 Solvent (Solv-9) 0.10

[0208]

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[0209]

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The photosensitive material 001 was processed into a roll having a width of 127 mm, and imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd. On the other hand, a solution (40 mmol / L) was prepared by adding or not adding the compound (A-1) to a bleach-fix solution (Brix) (tank solution and replenisher) described in detail below. Further, a color developing solution and a rinsing solution described in detail below are used. As the bleach-fixing solution, two types of the compound (A-1) added and not added are used. Two types of continuous processing (running test) were performed until the replenishment of the color developing tank was doubled in the processing step (running test liquids A and B). Processing process Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Triethanolamine 11.6 g 11.6 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonic acid 0.5 g 0.5 g Potassium chloride 10.0 g-Potassium bromide 0.040 g 0.010 g Triazinylaminostilbene Fluorescence 2.5g 5.0g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl ) -3-Methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g Potassium carbonate 26.3 g 26.3 g Water was added to the mixture, and 1000 ml 1000 ml pH (at 25 ° C.) / Adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] 800 ml of water 800 ml of ammonium iron (III) ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g of ethylenediaminetetraacetic acid 2.8 g m-carboxymethylbenzene full Finic acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / L) 107.0 mL 214.0 mL Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water 1000 mL 1000 mL pH (25 ° C / acetic acid) And ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] Deionized water (conductivity 5 μs / cm or less) 1000 ml 1000 ml pH 6.5 6.5

The photographic papers (000) and (001) were exposed for 1 second through optical wedges and blue, red, and red filters. The following two types of photographic paper after the exposure were subjected to the following development using the following developer, bleach-fix, and rinse after the continuous processing (running test). At that time, the following bleach-fix solutions were prepared. 1. 1. Bleach-fix solution before continuous processing (for comparison) 2. Bleach-fix solution after completion of continuous processing (for comparison) Compound (A-1) was added to the bleach-fix solution of (2) above (40 m
mol / L). For each of the cases using the above liquids 1, 2, and 3, the processing was performed at the same temperature and processing time as in the continuous processing using a small automatic developing machine. The stain was evaluated.

(Evaluation of Color Reproducibility) The densities of magenta and yellow at a density of 2.0 were measured for a sample which was exposed to a single color of cyan. The lower the magenta or yellow density in the cyan density, the less color turbidity and the better the color reproducibility. (Evaluation of stain after storage under moist heat) The reflection density of yellow, magenta and cyan of the photographic paper after the treatment was measured to obtain a characteristic curve, and the minimum density (Dmin) was obtained. Next, the Dmin after storage of this photographic paper at 60 ° C. and 70% for 15 days was measured, and the difference Dmin between the Dmin before and after storage was determined. The smaller the value of Dmin, the smaller the increase in stain due to wet heat storage. Table 3 shows the above results.

[0216]

[Table 3]

As shown in the results in Table 3, when the image was processed with the developing solution after the continuous processing, the stain deteriorated when the image was stored under wet heat as compared with the processing with the developing solution before the continuous processing. Stain was improved when added to the bleach-fix solution. Further, the results of this example show that when a pyrrolotriazole cyan coupler is used, color reproducibility is excellent, and
It shows that the compounds of the present invention are also more effective in improving stain.

Example 2 A3 size photographic paper (001) was exposed imagewise using a stretching machine. The following processing steps, color developing solution (C
D-2) A running test was performed using a rinsing solution until the tank was replenished with twice the capacity of the color developing solution. However, the running test was carried out for two cases of a bleach-fix solution (tank solution and replenisher) with or without the compound of the present invention.

Processing Step Temperature Time Replenishment Amount Tank capacity (liter) Color development 47 ° C. 20 seconds 35 ml 2 Bleaching and fixing 40 ° C. 20 seconds 38 ml 1 rinse 40-45 ° C. 3.2 seconds-0.5 rinse 40-45 ° C. 0 second-0.5 rinse 40-45 ° C 2.0 seconds-0.5 rinse 40-45 ° C 2.0 seconds-0.5 rinse 40-45 ° C 3.2 seconds 80ml 0.5 Drying 80 ° C for 10 seconds (Rinsing → 5 tank countercurrent method)

In the above treatment, the rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use. In addition,
In order to reduce the crossover time between the rinses, a blade was installed between the tanks, and the photosensitive material was passed between them. In each step, the spray amount was set to 1 using the apparatus described in the above embodiment.
The circulating liquid was sprayed at a setting of 4 to 6 liters / min per tank.

[Color Developer (CD-2)] Tank Solution Replenisher Water 700 ml 700 ml Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene -Disodium 4,6-disulfonate 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 15.8 g-Potassium bromide 0.04 g-Potassium carbonate 27.0 g 27.0 g Sodium sulfite 0 0.1 g 0.1 g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 18.0 g 35.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate Salt 8.0 g 23.0 g Na-bis- (2,4-disulfonatoethyl- , 3,5-triazyl-6) -diaminostilbene-2,2-disulfonate 5.0 g 5.0 g Water was added 1000 ml 1000 ml pH (25 ° C.) 10.35 12.80 (Each treatment solution was (The pH was set in the same way as the color developer tank solution or replenisher)

[Bleaching-fixing solution] <Tank solution of bleach-fixing solution> The following first replenisher 260 ml The following second replenishing solution 290 ml Water was added to 1000 ml pH (25 ° C.) 5.0 <Replenisher> (First replenisher) Water 150 ml Ammonium sulfite monohydrate 226 g Ethylenediaminetetraacetic acid 7.5 g Ammonium bromide 30 g Ammonium thiosulfate (700 g / liter) 340ml Add water 1000ml pH (25 ° C) 5.82

(Second Replenisher) Water 140 ml Compound (A-1) 0 g (liquid-4) Compound (A-1) 30 g (liquid-5) 11.0 g ethylenediaminetetraacetic acid iron (III) ammonium ethylenediaminetetraacetate 384 g acetic acid (50%) 230 ml water was added. 1000ml pH (25 ° C) 3.35

Replenishing amount of bleach-fixing solution (total amount of 38 ml per m ^{2 in the following} amount) First replenishing solution 18 ml Second replenishing solution 20 ml [Rinse solution] Ion-exchanged water (3 ppm each for calcium and magnesium)
Less than)

The photographic paper used in Example 1 (00
1) and the color image stabilizer (C) used in photographic paper (001)
The printing paper (002) in which the amount of pd-9) was doubled was used. Exposure was performed under the same conditions as in Example 1, and image development was performed by performing development, bleaching, fixing, and stabilization processes using a developer and the like after the two types of continuous processing. The amount of the main drug remaining in the image was measured, and the stain after storage under moist heat was evaluated. Table 4 shows the results. In Table 4, "Liquid-4" refers to the compound (A
Developer after continuous processing without adding -1)
The term “solution-5” means a developer, a bleach-fixer, and a rinse after the compound is added and subjected to continuous processing.

[0226]

[Table 4]

As is evident from the results in Table 4, the addition of the compound (A-1) of the present invention to the bleach-fixing solution makes it possible to reduce the amount of the remaining main drug and to improve the stain after storage under wet heat. did it. On the other hand, even in the printing paper (002) in which the amount of the color image stabilizer in the cyan coupler-containing layer was increased, no sufficient improvement was obtained when the compound of the present invention was not used in the bleach-fixing solution.

Example 3 In the same manner as in Example 2 except that the compound (A-1) was not added, a 1 L portion of each of the developer, the bleach-fixer, and the rinse was obtained after the running test. As shown in Table 5 below, various compounds were added to a bleach-fix solution (Brix solution) and / or a stabilizing solution to obtain a processing solution. Processing was performed by a small-sized automatic processing machine to form an image. The exposure at this time was the same as in Example 1. The remaining main drug amount, stain after wet heat storage, and sharpness were evaluated below. (Evaluation of Sharpness after Storage under Wet Heat) Next, a rectangular pattern having a density difference of 0.5 and having a changed spatial frequency deposited on a glass substrate was brought into close contact with each photographic paper, and exposed through a red filter. A similar process was performed. The density of the obtained rectangular image was precisely measured with a microdensitometer, and a spatial frequency (CTF value) at which the density value became 0.5 was obtained as a standard of sharpness. Next, the CTF value after storing this photographic paper at 60 ° C. and 70% for 15 days was determined, and the difference ΔCTF between the CTF values before and after storage was determined. The smaller the value of ΔCTF, the smaller the degradation of the resolution due to the moist heat storage.

[0229]

[Table 5]

[0230]

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Example 4 In this example, the solubility of the compound (A-1) in a bleach-fixing solution and its stability, that is, whether the compound was precipitated after the solution was allowed to stand, were evaluated. Compound (A-1),
(A-3) and (A-9) were added to the first replenisher and the second replenisher of the bleach-fix solution of Example 2 at 150 mmol / L, and the solubility and the subsequent aging were examined. Similarly, comparative compounds 1 and 2 were examined. Put the dissolved and partially dissolved in a PET bottle with a sealed stopper,
The mixture was allowed to stand at 0 ° C. for 4 weeks, and it was observed whether or not precipitation of the compound occurred. Table 6 shows the results.

[0232]

[Table 6]

As can be seen from the above table, the compounds (A-1), (A-3) and (A-9) of the present invention did not dissolve in the first replenisher but dissolved in the second replenisher. No compound precipitation occurs even after standing for 4 weeks. On the other hand, in the case of Comparative Compound 1, it does not dissolve in the second replenisher and dissolves in the first replenisher, but when this solution is left for 4 weeks, precipitation occurs.
Further, Comparative Compound 2 was not completely dissolved in the first replenisher, precipitated after standing for 4 weeks, and did not dissolve in the second replenisher. Therefore, the compounds (A-1), (A
It can be seen that when (3) and (A-9) are used for the second replenisher, they can be stably stored without precipitation even at the beginning of dissolution or after standing for a long period of time. In contrast, for the comparative compound, one compound was dissolved in the first replenisher, but the solution was not stable.

Example 5 An experiment was carried out in the same manner as in Example 1 except that the exposure conditions for photographic paper (000) and (001) were changed to scanning exposure, and similar results were obtained. Example 6 This example shows an example in which the components of the first replenisher and the second replenisher in Example 2 are processed into tablets and used. Hereinafter, the composition of the first replenisher and the composition of the second replenisher are shown. [First replenisher composition] Sodium sulfite 150 g Ethylenediaminetetraacetic acid 7.5 g Ammonium bromide 30 g Ammonium thiosulfate 240 g Water-soluble starch 40 g [Second replenisher composition] Compound (A-1) 30 g Ethylenediaminetetraacetic acid 11.0 g Ethylenediaminetetraacetic acid (III) Ammonium 384 g Sodium acetate 140 g Water-soluble starch 40 g Each of the mixtures of the above composition is milled in a commercial Rimmer mill mill to an average particle size of 10 μm. After granulating the fine powder by spraying 20 ml of water for about 5 minutes at room temperature in a commercially available fluidized bed spray granulator, the granulated material is dried at 55 ° C. for 30 minutes to almost completely remove moisture. Remove. Fine particles of less than 200 μm and excessive particles of more than 1000 μm were removed from the obtained granules by a conventional method. Next, the obtained granulated product was toughened by Kikusui Seisakusho in a room conditioned at 25 ° C. to 40% RH or less.
Using a tableting machine modified from 27HU, the filling amount per tablet was 7.5 g in a die having a diameter of 25 mm, and the compression pressure was 800.
Tableting was performed at Kg / cm ² to obtain 100 fixing replenishment tablet samples 1 to 12. A developing process was performed in the same manner as in Example 2 except that the bleach-fixing process was performed using the tablets for the first replenisher and the tablets for the second replenisher thus prepared. The result was obtained.

[0235]

According to the present invention, when a series of processing such as development, bleaching and fixing is performed by rapid or ultra-rapid processing, the developing agent easily remains in the image layer as compared with the case where the processing is performed at a normal speed. Accompanying this, stain occurs when storing the image in moist heat,
By performing at least one step of desilvering treatment, washing with water and / or stabilization in the presence of the compound represented by the general formula [A] as in the present invention, the residual active substance in the image is sufficiently reduced. As a result, it is possible to prevent the occurrence of stain after storage under moist heat. In addition, when a conventional active ingredient removal accelerator is used, the accelerator tends to remain in the image, and the sharpness of the image after storage under moist heat tends to deteriorate (generation of bleeding). Further, precipitation occurs when the replenisher is stored. Although there was a problem with the replenisher stability, the deterioration of sharpness and the problem of the replenisher stability as described above were avoided by using the active ingredient removal accelerator of the present invention. In addition, when the compound of the formula (I) is used as the cyan coupler, there is a problem that the residual principal agent stain is easily deteriorated as compared with the case where the conventional cyan coupler is used. The combined use with the agent solved the problem of the residual active drug stain, and as a result, remarkable color reproducibility was achieved.

Claims (7)

[Claims] 1. A support comprising at least one layer each of a yellow-sensitive photosensitive silver halide emulsion layer, a magenta-sensitive photosensitive silver halide emulsion layer, and a cyan-sensitive photosensitive silver halide emulsion layer on a support. An image forming method comprising drying a silver halide color photographic light-sensitive material having at least one non-color-forming hydrophilic colloid layer after image exposure, followed by development, desilvering, washing with water and / or stabilization. A color image forming method, wherein at least one of the steps of desilvering, washing and / or stabilizing is performed in the presence of a compound represented by the following general formula [A]. Embedded image In the formula [A], R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an aralkyl group. The total number of carbon atoms of R ¹ + R ² is 3-8, and R ¹ and R ² are not simultaneously hydrogen atoms, R ¹ and R ² may form a ring bonded to each other. 2. The color image forming method according to claim 1, wherein the desilvering step is performed in the presence of the compound represented by the general formula [A]. 3. The method according to claim 1, wherein at least one of the cyan-color-forming photosensitive silver halide emulsion layers contains at least one cyan dye-forming coupler selected from the compounds represented by the following general formula (I). Or the color image forming method according to 2. Embedded image Wherein ^{(I), Z a, Z} b each -C (R ⁵⁾ = or represents -N =. However, either Z ^a or Z ^b is −
Is N =, the other is -C (R ⁵⁾ is =. R ³ and R
⁴ has a Hammett's substituent constant σ _p value of 0.20
Represents the above electron-withdrawing group, and the sum of the σ _p values of R ³ and R ⁴ is 0.65 or more. R ⁵ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. The group of R ³ , R ⁴ , R ⁵ or X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. 4. At least one layer of a cyan-color-forming photosensitive silver halide emulsion layer, or at least one of the non-color-forming hydrophilic colloid layers, or at least one of the cyan-color-forming photosensitive silver halide emulsion layers and the non-color-forming silver halide emulsion layer 4. The color image forming method according to claim 1, wherein at least one of the hydrophilic colloid layers contains at least one compound represented by the following general formula (II). Embedded image In formula (II), R ^a1 and R ^a2 each independently represent a hydrogen atom, an alkyl group or an aryl group. R ^a3 and R ^a4 represent a hydrogen atom,
Represents an alkyl group or an aryl group. R ^a5 represents an aryl group. However, ^Ra1 , ^Ra2 , ^Ra3 , ^Ra4 and ^Ra5
Does not become 13 or less. 5. The color image forming method according to claim 1, wherein the silver halide emulsion is a high silver chloride emulsion having a silver chloride content of 95 mol% or more. 6. The color image forming method according to claim 1, wherein the exposure is performed by scanning exposure. 7. A processing composition for desilvering a silver halide color photographic light-sensitive material, which comprises at least one compound represented by the formula [A].