JP2863050B2 - Color image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method, and more particularly to a color image forming method capable of shortening a processing time and significantly improving color reproducibility.

[0002]

2. Description of the Related Art Generally, the basic steps of processing a color photographic light-sensitive material include a color development step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to form silver, and the oxidized color developing agent reacts with a color forming agent (coupler) to give a dye image. In the subsequent desilvering step, silver produced in the color developing step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved by a silver ion complexing agent commonly called a fixing agent. You. Through this desilvering step, only a dye image is formed on the color photographic material.

The above desilvering step is carried out in two baths, a bleach bath containing a bleaching agent and a fixing bath containing a fixing agent, and in one bath using a bleach-fixing agent in which a bleaching agent and a fixing agent coexist. May be done. The actual development process includes various auxiliary steps such as to maintain physical quality or to improve image storability. For example, there are a dura bath, a stop bath, an image stabilizing bath, and a washing bath. In recent years, with the spread of small in-store processing service systems called minilabs,
There has been a strong demand for shortening the time required for the above-mentioned processing and reducing replenishment in order to quickly respond to processing requests from customers and to reduce maintenance work of these processing machines.

As a means for speeding up the color development process, a method of increasing the pH of the developer and the processing temperature has been tried.
The interlocking of photographic performance during continuous processing was large, and the stability of the developing solution was also deteriorated, which was not suitable for practical use.

Attempts have been made to increase the temperature of the color developing solution or to speed up the color developing step by increasing the concentration of the color developing agent in the color developing solution. However, the supply of the developing agent is limited by the shortening of the color development time, and is delayed compared to the development of the layer (upper layer) far from the support, resulting in a large loss of color balance and markedly degraded color reproducibility. I knew it would.

In general, a photographic light-sensitive material for a color negative is required to have high sensitivity. Therefore, a light-sensitive material containing silver iodide in an average of 2 to 20 mol% is used as a color negative light-sensitive material. From the viewpoint of the speed and hue of the silver iodide-containing photographic material, 2-methyl-4- [N-ethyl-N- (β -Hydroxyethyl) amino] aniline (P-5).

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color image forming method which can shorten the color development time of a color photographic material containing silver iodide and has a good color balance and excellent color reproducibility. It is in.

[0008]

The above objects have been achieved by the present invention described below. That is, at least one red-sensitive silver halide emulsion layer on a support,
A silver halide color photographic light-sensitive material having a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer and having an average silver iodide content of 2 to 20 mol% in all the color-sensitive silver halide emulsion layers. In a color image forming method for color development with a developer,
The sum of the weight of the coupler and the high boiling point organic solvent contained in the entire hydrophilic colloid layer in which the light-sensitive material is farther from the support than the red-sensitive silver halide emulsion layer closest to the support is 1 g / m ² or more. a 10 g / m ^2, was achieved by a color image forming method characterized in that the developing solution contains at least one aromatic primary amine color developing agent represented by the following general formula (D).

[0009]

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In the formula (D), R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched alkyl group having a main chain of 3 to 8 carbon atoms. Represents a hydroxyalkyl group. R ₂ is a straight-chain or branched unsubstituted alkylene group having 3 to 8 carbon atoms whose main chain has 3 to 8 carbon atoms, or a straight-chain or 3 to 8 carbon atoms whose main chain has 3 to 8 carbon atoms. Represents a branched hydroxyalkylene group. R
₃ is a linear or branched alkyl group having a carbon number of 1-4, or
Or an alkoxy group . These groups may be further substituted with a substitutable group.

In the present invention, the weight of the coupler and the high-boiling organic solvent in the hydrophilic colloid layer means the amount of the dye-forming coupler (development inhibitor, desilvering accelerator or precursor thereof released) contained in the layer. including) and indicates a total coating weight per 1 m ² of the high-boiling organic solvents functional couplers such as.

Generally, as a developing agent having high hydrophobicity,
Developing agents having no hydrophilic group at the N-substitution such as 4-amino-3-methyl-N, N-diethylaniline and 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline are known. However, these compounds are easily distributed to an oil-soluble phase containing a coupler and the like, which has been considered to enhance the developability and to shorten the color development time (US Pat. No. 3,656,950; 3,656,925 and 4,035,188). However, development of the highly hydrophobic developing agent was delayed more toward the lowermost layer in the light-sensitive material, the color balance was largely lost, and only an image having extremely poor color reproducibility was obtained. Further, it is known as a so-called abnormal concentration effect that, when the concentration of the developing agent having a high hydrophobicity becomes higher than a certain concentration, neutral semiquinone of the developing agent is adsorbed on the surface of silver halide grains to suppress development. (D. Neuberger and HC Roberts, Ph
otogr. Sci. Eng. 19, 327, 1975), in particular, it was considered to be an unsuitable developing agent for shortening the color development time by increasing the concentration of the developing agent. The developing agent of the present invention has higher hydrophobicity than the above-mentioned commonly used developing agent (P-5), and thus has the above-mentioned problem.

As described above, it has been found that the developing agent of the present invention has very high development activity, but has low diffusivity, and cannot be used unless the development delay of the lower layer is eliminated. The present inventor has considered that the substance that greatly affects the diffusibility of the developing agent is affected by the coupler and the high-boiling organic solvent as a substance that reduces the diffusibility of the developing agent in the layer up to the lower layer. Generally, the coupler is dispersed in gelatin as an oil-soluble phase using a high-boiling organic solvent. Therefore, the diffusion coefficient of the developing agent of the present invention was examined for a gelatin film, a gelatin film in which an oil-soluble phase was dispersed, and a film in which an oil-soluble phase was dispersed and also containing a silver halide emulsion (J. Appl. Polym. Sci, 30, 207
5 (1985)). As a result, the film thickness of the negative photosensitive material is usually 28 μm or less, and at such a film thickness, the diffusion of the developing agent of the present invention depends on the total weight of the coupler and the high boiling point organic solvent contained in the gelatin film. It turns out that it is almost decided. We have:
Based on this finding, the present inventors worked on the development of a technique that makes full use of the developing agent of the present invention, and developed the present invention.

The total weight of the coupler and the high boiling organic solvent is preferably 1 to 8 g / m ² , and 1.5 to 5 g / m ^2.
Further preferably / m ^2, and most preferably 2.0~3g / m ^2.

Surprisingly, the red-sensitive silver halide emulsion layer closest to the support contains at least one cyan dye-forming coupler represented by the following general formula (II) or (III). The color balance was improved, and excellent color reproducibility was achieved.

[0016]

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In the formula (II), R ₁ is -CONR ₄ R ₅ , -S
_{O 2 NR 4 R 5, -NHCOR} 4, -NHCOOR 6, -N
_{HSO 2 R 6, -NHCONR 4 R} 5 or -NHSO ₂ N
R _{4 and} R ₅ , R ₂ is a group capable of being substituted on a naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, X is a hydrogen atom or an oxidized aromatic primary amine developer. Each represents a group capable of leaving by the coupling reaction of Where R
₄ and R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R ₂ may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may combine with each other to form a ring. Further, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X bonded to each other via a divalent or divalent or higher valent group may be formed.

[0018]

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In the formula (III), R ₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₂ represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.

Further, at least one of the green-sensitive silver halide emulsion layers above the red-sensitive silver halide emulsion layer contains at least one magenta dye-forming coupler represented by the following general formula [M]. This accelerated the development of the lower red-sensitive emulsion layer.

[0021]

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In the formula [M], R ₁ represents a hydrogen atom or a substituent. Z represents a group of nonmetal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).
X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent.

Further, the red-sensitive emulsion layer of the present invention contains a cyan dye-forming coupler represented by the general formula (II) or (III), and the green-sensitive emulsion layer of the present invention has a general formula [M]
At least one magenta dye-forming coupler represented by
Most preferably, it contains a species.

Hereinafter, the general formula (D) will be described in detail. In the general formula (D), R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched hydroxy group having 3 to 8 carbon atoms whose main chain is 3 to 8 carbon atoms. Represents an alkyl group. Here, the main chain refers to a linking group between the connecting nitrogen atom and the hydroxyl group, and R ₁
Has a plurality of hydroxyl groups, the one having the least number of carbon atoms. Specific examples of R ₁ include:
For example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl, n-hexyl, neopentel, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 4-hydroxypentyl, 3-hydroxybutyl,
4-hydroxy-4-methylpentyl, 5,6-dihydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyoctyl, 8-hydroxyoctyl and the like.

R ₂ has 3 carbon atoms whose main chain has 3 to 8 carbon atoms.
Represents a straight-chain or branched unsubstituted alkylene group of -8, or a straight-chain or branched hydroxyalkylene group of 3-8 carbon atoms having a main chain of 3-8 carbon atoms. Here, the main chain refers to a connecting chain of the connecting nitrogen atom and the hydroxyl group described in the general formula (D), and when R ₂ has one or more hydroxyl groups, The hydroxyl group bonded on the carbon atom having the least carbon number by counting corresponds to the hydroxyl group described in the general formula (D), and its connecting chain is the main chain. Specific examples of R ₂ include, for example trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, 3-methyl pentamethylene, 2-methylpentamethylene, 2-ethyltrimethylene, 3- (2-hydroxyethyl) trimethylene,
6- (1,2-dihydroxyethyl) hexamethylene and the like.

In the general formula (D), R ₁ and R ₂ are
R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and R ₂ is a straight-chain or branched unsubstituted alkylene group having 4 to 6 carbon atoms in the main chain, or R ₁
Is a straight-chain or branched hydroxyalkyl group having 4 to 8 carbon atoms in which the main chain has 4 to 8 carbon atoms, and a straight-chain or branched hydroxyalkyl group having 4 to 8, particularly 4 to 6 carbon atoms in the main chain of R _2. It is preferably a branched unsubstituted alkylene group. General formula (D)
More preferably, R ₁ is a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and R ₂ is a tetramethylene group.

In the general formula (D), R ₁ has 1 to ₁ carbon atoms.
In the case of 6 straight-chain or branched unsubstituted alkyl groups, the number of carbon atoms is more preferably 1 to 4. Among them, a methyl group, an ethyl group and an n-propyl group are particularly preferred, and an ethyl group is most preferred.

[0028] R ₃ represents a linear or branched alkyl group or alkoxy group, having a carbon number of 1-4. These groups may be further substituted with a substitutable group. More particularly R ₃ is a linear or branched alkyl group (e.g. methyl carbon number 1 to 4, ethyl, n- propyl, isopropyl, sec- butyl, 3-hydroxypropyl, 2-
Methanesulfonamide ethyl), or an alkoxy group (e.g. methoxy, ethoxy, isopropoxy), etc. can be mentioned. R ₃ is Ru <br/> Oh alkyl group or alkoxy group. More preferably, R ₃ is preferably a straight-chain or branched alkyl group not substituted with a substituent, more preferably a straight-chain alkyl group, and particularly preferably a methyl group or an ethyl group. Particularly preferred is a methyl group.

Next, specific examples of the representative developing agent represented by formula (D) in the present invention will be shown, but the present invention is not limited by these.

[0030]

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[0031]

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[0032]

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Among the compounds represented by formula (D), the most preferred compound is exemplified by compound D-12.

The compound represented by the general formula (D) may be stored as a free amine. In general, the compound is prepared and stored as a salt of an inorganic acid or an organic acid, and is added to the treatment solution only when the free amine is added. Is preferable. Examples of the inorganic and organic acids that form the salt of the compound of the formula (D) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid. Among these, a salt of sulfuric acid or p-toluenesulfonic acid is preferable, and salt formation as a salt with sulfuric acid is most preferable. For example, Exemplified Compound D-12 is obtained as a sulfate, and its melting point is 112 to 114 ° C (water-
Recrystallized from ethanol), and Exemplified Compound D-2
Is also obtained as a sulfate, the melting point of which is 158 to 160 ° C.
(Recrystallized from water-ethanol). The amount of the color developing agent of the present invention to be used is preferably 0.3 mmol to 100 mmol, more preferably 3 mmol to 80 mmol per liter of developer.
Mmol, more preferably from 20 to 75 mmol, particularly preferably from 25 to 60 mmol. The processing temperature of the developer is 20 to 60C, preferably 30 to 55C, more preferably 42 to 52C, and particularly preferably 45 to 50C. The color developing agent of the present invention is, for example, Journal of the American Chemical Society 73, 3100
Page (1951), British Patent No. 807,899, and can be easily synthesized.

Synthesis Example (Synthesis of Exemplified Compound (D-12)) According to the following synthesis scheme, Exemplified Compound (D-12)
Was synthesized.

[0036]

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Synthesis of A Tetrahydrofuran 73 was prepared according to the method described in Journal of the Chemical Society, page 1536 (1954).
From 2 g, 831 g of acetyl bromide and 0.3 g of zinc chloride,
1137 g of A was synthesized. 87 yield from acetyl bromide
%.

Synthesis of C To 825 g of B, N, N-dimethylacetamide 165
0 ml, 250 g of Al and 538 g of sodium hydrogen carbonate were added, and stirring was continued at 120 ° C. for 3 hours. Next, after cooling, 3300 ml of ethyl acetate was added, and the mixture was washed with water (3000 ml).
× 2), then washed with saturated saline (3000 ml × 1)
Thereafter, the ethyl acetate was distilled off under reduced pressure to obtain an oil 149 containing C.
6 g were obtained. Synthesis of D To 1,442 g of C, 7200 ml of methanol was added, and an aqueous solution of 254 g of sodium hydroxide dissolved in 1,400 ml of water was added dropwise with stirring under ice cooling. After stirring at room temperature for 6 hours, 2800 ml of water was added and extracted with ethyl acetate (300 ml).
0 ml × 1), and the ethyl acetate layer was washed with water (2800 ml).
× 1) and then washed with a saturated saline solution (2800 ml × 1), and then ethyl acetate was distilled off under reduced pressure.
4 g were obtained.

Synthesis of E 570 ml of concentrated hydrochloric acid and 643 g of D were dissolved in 3100 ml of water, and sodium nitrite 182 was added thereto while stirring under ice cooling.
g of water in 360 ml of water was added dropwise over 1 hour and 30 minutes. Thereafter, sodium hydrogen carbonate was added until the reaction system was neutralized, extracted with ethyl acetate, and ethyl acetate was distilled off under reduced pressure to obtain 616 g of an oil containing compound E.

Synthesis of Exemplified Compound (D-12) To 237 g of E, 480 ml of ethanol and 1.0 g of 10% palladium carbon were added, and the mixture was stirred without heating in an autoclave. After the catalyst was separated by filtration using Celite as a filter aid, the catalyst was dropped into a mixed solution of 89.5 g of concentrated sulfuric acid, 100 ml of water and 200 ml of ethanol, and the precipitated crystals were collected by filtration. The crystals were dissolved in 114 ml of water while heating, 11 g of activated carbon was added, and stirring was continued at 80 to 90 ° C for 1 hour. Activated carbon was filtered off using Celite as a filter aid, 700 ml of ethanol was added, and the precipitated crystals were collected by filtration to give 198 g of the monosulfate monohydrate of the desired exemplary compound (D-12) as colorless crystals. Obtained. 49 g from B,
Melting point: 112-114 ° C.

The color developing agent of the present invention is preferably used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compounds to be combined are shown below, but are not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 2-amino-5- (N, N-diethylamino)
Toluene P-3 2-amino-5- (N-ethyl-N-laurylamino) toluene P-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline P-5 2-methyl-4 -[N-ethyl-N- (β-hydroxyethyl) amino] aniline P-6 4-amino-3-methyl-N-ethyl-N-
[Β- (methanesulfonamido) ethyl] aniline P-7 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline P-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline P-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline

As the compound to be combined, among the above-mentioned p-phenylenediamine derivatives, particularly preferred is the exemplified compound P
-5 or P-6. In addition, these p-phenylenediamine derivatives and sulfates, hydrochlorides, sulfites, p-
Toluenesulfonate, nitrate, naphthalene-1,5-
It is commonly used in salts such as disulfonates. The amount of the developing agent used in combination is 1/1 to 1 mol of the developing agent of the general formula of the present invention unless the effect of the present invention is impaired.
It is preferable to use 0 to 10 mol. The color developing solution used in the present invention is generally alkaline,
Preferably, it is an alkaline aqueous solution having a pH of 9 to 12.5.

The developing agent of the present invention has high hydrophobicity and excellent development activity as compared with P-6, which is currently widely used as a developing agent for color negatives, and also suppresses the development caused by the developing agent having high hydrophobicity. A developing agent.

In the color developer of the present invention, compounds which directly preserve the aromatic primary amine color developing agent of the present invention are disclosed in JP-A-63-5341 and JP-A-63-106655.
Or the various hydroxylamines described in JP-A-4-144446, the hydroxamic acids described in JP-A-63-43138, the hydrazines and hydrazides described in JP-A-63-146041, 63-44657 and 63-64 Phenols described in JP-A-58443, 63-
Α-hydroxyketones and α-aminoketones described in No. 44656, various sugars described in No. 63-36244, and the like. Further, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
Monoamines described in JP-A-3-27841 and JP-A-63-25654, JP-A-63-30845, JP-A-63-14
No. 640, No. 63-43139, diamines described in JP-A Nos. 63-21647, 63-26655 and 63-44655, polyamines described in No. 63-44655, and No. 63
Nitroxyl radicals described in JP-A-53551, 63
Alcohols described in JP-A-43140 and JP-A-63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239947 can be used. Other preservatives are disclosed in
Various metals described in Nos. 44148 and 57-53749, salicylic acids described in 59-180588, alkanolamines described in 54-3582, and polyethyleneimines described in 56-94349. And an aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544, if necessary.
Particularly preferred preservatives are described in JP-A-3-144446.
And hydroxylamines represented by the general formula (I), and among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferable. The addition amount of these preservatives is 20 to 200 mmol, preferably 30 to 150 mmol, per liter of the color developer.

Other additives described in JP-A-3-144446 can be used in the color development of the present invention. For example, examples of the buffer for maintaining the pH include carbonic acids, phosphoric acids, boric acids, and hydroxybenzoic acids on page 9 of the publication. As the chelating agent, various aminopolycarboxylic acids, phosphonic acids, and sulfonic acids on the same page, preferably ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylene phosphonic acid) and catechol-3,5-disulfonic acid are preferred. The color developer uses these buffers to adjust the pH to 10-12.
Preferably, it is maintained between 5. More preferably pH
Is 10 to 11.5. As the development accelerator, for example, various additives described on pages (9) to (10) of the publication can be used. The same publication (1)
0) Halogenated ions and organic antifoggants described on page 0). In particular, the bromide ion concentration is high when the concentration of the developing agent in the color developer is as high as 20 mmol / L or more.
When processing at a high temperature of 2 ° C. or more, 25 mmol to 80 mmol /
Higher ones such as liters are preferred. Further, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

For color development, low replenishment processing is preferred, and 75 ml to 5 ml / m ² processing of silver halide color photographic light-sensitive material.
A replenishing volume of 00 ml is preferred, more preferably 75 ml to 3 ml.
The volume is 50 ml, more preferably 75 ml to 200 ml. The processing time of color development is preferably from 30 seconds to 3 minutes and 15 seconds, more preferably from 35 seconds to 2 minutes and 30 seconds, particularly preferably from 40 seconds to 1 minute and 20 seconds.

In the present invention, the color-developed photosensitive material is subjected to a desilvering process. The desilvering process referred to here basically comprises a bleaching process and a fixing process, but is constituted by a bleach-fixing process in which these processes are performed simultaneously and a combination of these processes. Examples of the bleaching agent include the above-mentioned JP-A-3-14444.
As described on page (11) of JP-A-6, ferric aminopolycarboxylate or a salt thereof is preferably used. Further, the compounds described in JP-A-4-127145 and 4-
Carbamoyl-based bleaching agents described in
A bleaching agent having a hetero ring described in JP-A-174432 is also preferably used. In the desilvering bath of the present invention, in addition to the bleaching agent, a rehalogenating agent, a pH buffering agent and known additives described in JP-A-3-144446, page (12), aminopolycarboxylic acids, and organic Phosphonic acids and the like can be used. In the present invention, various bleaching accelerators can be added to the bleaching solution or its pre-bath. Such bleaching accelerators are described, for example, in US Pat. No. 3,893,858 and German Patent 1,29.
No. 0,821, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-50-140129, thiazolidine derivatives described in US Pat. No. 3,706,561, thiourea derivatives described in US Pat. No. 3,706,561, JP-A-58-16235 Iodides, polyethylene oxides described in German Patent Specification No. 2,748,430, JP-B-45
For example, a polyamine compound described in JP-A-8836 can be used. Particularly preferably, British Patent No. 1,13
Mercapto compounds as described in JP-A-8,842 and JP-A-2-190856 are preferred.

In a processing solution having a fixing ability, sulfites (for example, sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (for example, sodium acetaldehyde bisulfite, particularly preferably a compound described in JP-A-3-158848) or JP-A-1
And a sulfinic acid compound described in JP-A-231051. Furthermore, various fluorescent whitening agents, defoamers or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Cyclohexanediaminetetraacetic acid, 1,
2-propylenediaminetetraacetic acid can be mentioned.

The processing solution having a fixing ability preferably contains a compound having a pKa in the range of 6.0 to 9.0 for adjusting the pH or as a buffer. As these compounds, imidazole compounds are preferred. The imidazole compound is preferably contained in an amount of 0.01 mol / liter or more. A more preferable addition amount of the imidazole compound is 0.1
To 10 mol / l, particularly preferably 0.2 to 3 mol / l.
Liters. The imidazole compound refers to imidazole and derivatives thereof, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, and a halogen atom. Further, the alkyl group, alkenyl group, and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom, or the like. The preferred total carbon number of the substituents of imidazole is 1 to 6, and the most preferred substituent is a methyl group. Specifically preferred compounds are imidazole,
2-Methyl-imidazole, 4-methyl-imidazole, the most preferred compound being imidazole.

The processing solution having a fixing ability is preferably subjected to silver recovery processing. In the case of a processing solution having bleaching ability, the overflow is stocked and reused using a regenerant. The solution having a fixing ability and the solution having a bleaching ability may be separately separated, or may be used as a bleach-fix solution. When the liquid having the fixing ability and the liquid having the bleaching ability are separated separately, the waste liquid is mainly a liquid having the fixing ability, or a liquid having the fixing ability is recovered in-line with silver, and the recovered waste liquid is discharged. In addition to performing the silver recovery in-line, the overflow may be collectively subjected to a silver recovery process, and the processed liquid may be recycled and reused. In the case of the bleach-fix solution, in-line silver is collected, the waste liquid after the collection is discharged, and the overflow of the bleach-fix solution is recycled and reused. Silver can be recovered from the processing solution having the fixing ability by a known method. Examples of the silver recovery method include an electrolysis method (described in French Patent No. 2,299,667) and a precipitation method (described in No. 52-73037, German Patent No. 2,331,220), ion exchange method (Japanese Patent Laid-Open No. 51-17114, German Patent No. 2,548,237), and metal replacement method (UK Patent No. 1,353,805
No.) is effective. These silver recovery methods are preferably performed in-line from the tank liquid because the rapid processing suitability is further improved. In the present invention, the processing temperature in the desilvering step comprising a combination of bleaching, bleach-fixing and fixing is from 40 to 60 ° C.
Preferably it is 40-55 degreeC. pH is 3.0-7.
0, preferably 4.0 to 6.0. The processing time of the desilvering step is preferably 4 minutes or less, more preferably 3 minutes or less.

After the processing step having the fixing ability, usually,
A water washing process is performed. After processing with a processing solution having fixing ability,
A simple treatment method of performing a stabilization treatment using a stabilizing solution without substantially performing water washing can also be used. The washing water used in the washing step and the stabilizing solution used in the stabilizing step are used to prevent water droplet unevenness when the photosensitive material is dried after processing.
Various surfactants can be included. Among them, it is preferable to use a nonionic surfactant, and particularly preferable is an alkylphenol ethylene oxide adduct. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14.
It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water and the stabilizing solution may contain various antibacterial agents and fungicides for preventing generation of water rust and mold generated on the photosensitive material after processing. In addition, it is preferable to include various chelating agents in the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Organic phosphonic acids such as N ', N'-tetramethylene phosphonic acid, and hydrolysates of a maleic anhydride polymer described in European Patent No. 345,172A1 can be exemplified. It is also preferable to include a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution in the washing water and the stabilizing solution.

The washing or stabilizing solution is desirably treated by a multistage countercurrent method. The multi-stage counter-current system may be used in a conventional transport system using a crossover rack. However, in order to improve the washing efficiency, for example, a washing bath as disclosed in It is particularly preferable to perform countercurrent water washing in a multi-chamber water washing system in which the liquid is squeezed.
The number of multi-chambers is required to be two or more, preferably three or more, and more preferably four or more. Further, it is preferable to increase the washing efficiency by using a reverse osmosis device. The specifications of the reverse osmosis device are as follows: water after permeation through the osmosis membrane is introduced into the bath after washing or stabilizing bath, and the concentrated liquid is preferably introduced into the preceding bath, most preferably the permeated water is introduced into the final bath, The concentrate is preferably introduced into the previous bath.

As the stabilizing solution used in the stabilizing step, a processing solution for stabilizing a dye image, for example, an organic acid or a pH of 3 to
A solution having a buffer capacity of 6, or a solution containing aldehyde (eg, formalin or glutaraldehyde) can be used. The stabilizing solution can contain all the compounds that can be added to the washing water, and if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, fluorescent brighteners, and hardening agents. Alkanolamines described in U.S. Pat. No. 4,786,583 and the like can be used.

The stabilizing solution contains a compound for stabilizing a dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, dimethylol urea, and N-methylol. N-methylol compounds such as pyrazole, organic acids and pH buffers are included. The preferred addition amount of these compounds is 0.001 to 0.02 mol per liter of the stabilizing solution,
It is preferable that the concentration of free formaldehyde in the stabilizing solution is low because scattering of formaldehyde gas is reduced. From such a point, as the dye image stabilizer, m-hydroxybenzaldehyde, hexamethylenetetramine, N-
N-methylolazoles described in Japanese Patent Application No. 3-318644 such as methylol pyrazole, and N-methylolazoles described in Japanese Patent Application No. 3-142708 such as N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine. Azolylmethylamines are preferred. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, alkanolamines described in US Pat. No. 4,786,583, It is also preferable to include a preservative which can be contained in the fixing solution or the bleach-fixing solution. Of these, sulfinic acid compounds (for example, benzenesulfinic acid, toluenesulfinic acid, and salts thereof such as sodium and potassium) described in JP-A-1-231051 are preferable. 1 × 10 ^-5 to 1 × 10 ^-3 mol per liter is preferred,
In particular, 3 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol is more preferable.

The pH of the stabilizing solution is preferably from 6 to 9, more preferably from 6.5 to 8. The replenishment amount of the washing step and the stabilization step is 1 to 5 of the amount brought in from the previous bath per unit area.
It is 0 times, preferably 1 to 20 times, more preferably 1 to 7 times. The processing time is preferably 2 minutes and 30 seconds or less, more preferably 1 minute and 30 seconds or less, in the total processing time of the washing and / or stabilizing step. Tap water can be used as the water used in the washing step and the stabilization step, but water, deionized to a Ca or Mg ion concentration of 5 mg / liter or less with an ion exchange resin, halogen, an ultraviolet germicidal lamp, etc. It is preferred to use more sterile water. Further, it is preferable to use a method in which the overflow solution in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a pre-bath, because the amount of waste liquid can be reduced.

In the process of the present invention, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher in order to correct concentration due to evaporation. Although there is no particular limitation on the specific method for replenishing water,
No. 54959 and No. 1-254960, a separate monitoring tank was installed from the bleaching tank, the amount of water evaporation in the monitor tank was determined, and the amount of water evaporation in the bleaching tank was calculated from the amount of water evaporation. However, a method of replenishing the bleaching tank with water in proportion to the amount of evaporation is disclosed in JP-A-3-248155 and JP-A-3-248155.
No. 9644, No. 3-249645, No. 3-24964
An evaporation correction method using a liquid level sensor or an overflow sensor described in Japanese Patent Application Laid-Open No. 6-206 is preferable. Water for correcting the evaporation of each processing solution may be tap water, but deionized water preferably used in the above-mentioned washing step,
It may be sterile water.

From the viewpoint of prevention of evaporation or deterioration of the liquid, the area (opening area) where the liquid comes into contact with air is preferably as small as possible. For example, assuming a value obtained by dividing the opening area (cm ² ) by the volume (cm ³ ) of the processing solution as the opening ratio, the opening ratio is preferably 0.01 (cm ⁻¹ ) or less, and 0.005 (cm ⁻¹ )
The following is more preferred.

The compound represented by formula (II) will be described below in detail. R ₁ is -CONR ₄ R _5, -S
_{O 2 NR 4 R 5, -NHCOR} 4, -NHCOOR 6, -N
_{HSO 2 R 6, -NHCONR 4 R} 5 or -NHSO ₂ NR ₄
Represents R _5, R _4, R ₅ and R ₆ each independently represents a total number of carbon atoms (hereinafter referred to as C number) of 1 to 30 alkyl group, a heterocyclic aryl group, or a C number of 2 to 30 C number of 6 to 30 Represents a ring group. R ₄ and R ₅ may also be hydrogen atoms.

R ₂ represents a group (including an atom; the same applies hereinafter) substitutable on the naphthalene ring, and k represents an integer of 0 to 3. As a representative example of R _2, a halogen atom (F, Cl,
Br, I), a hydroxyl group, a carbonyl group, an amino group, a sulfo group, a cyano group, an alkyl group, an aryl group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group,
Acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, sulfamoylamino group,
Examples include an alkoxycarbonylamino group, a nitro group, and an imide group. Examples of the case where k = 2 include a dioxymethylene group and a trimethylene group. (R ₂ ) _{k has} a C number of 0 to 30.

R ₃ represents a substituent, preferably represented by the following formula (II-1). Formula (II-1) R ₇ (Y) _m − In Formula (II-1), Y is>NH,> CO or> SO
₂ , m is an integer of 0 or 1, R ₇ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms,
A heterocyclic group of the formulas 2 to 30, -COR ₈ ,

[0062]

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Or —SO ₂ R ₁₀ Here, R ₈ , R ₉ and R ₁₀ have the same meanings as R ₄ , R ₅ and R ₆ , respectively. In R ₁ or R ₇ , —NR ₄ R ₅
Of R ₄ and R ₅ and R ₈ and R ₉ bind each other with a nitrogen-containing heterocyclic (e.g. pyrrolidine ring, piperidine ring, morpholine ring) of -NR ₈ R ₉ may form.

X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of an aromatic primary amine developing agent (hereinafter referred to as a leaving group; including a leaving atom; the same shall apply hereinafter), and representative examples of the leaving group. As a halogen atom,

[0065]

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A thiocyanate group, a heterocyclic group having 1 to 30 carbon atoms and having a nitrogen atom and bonded to a coupling active site (for example, succinimide group, phthalimide group, pyrazolyl group, hydantoinyl group, 2-benzotriazolyl group) is used. Can be mentioned. Here, R ₁₁ has the same meaning as R ₆ .

In the above, the alkyl group may be linear, branched or cyclic, and may contain a substituent (for example, a halogen atom, a hydroxyl group, an aryl group, a heterocyclic group) even if it contains an unsaturated bond. , An alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group), and as typical examples, methyl, isopropyl, isobutyl, t-butyl, 2- Ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl, 3- (2,4-di-
t-pentylphenoxy) propyl.

The aryl group may be a condensed ring (for example, a naphthyl group) or a substituent (for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
A cyano group, an acyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group).
Tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2
-Tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl, 4-t-butylphenyl.

The heterocyclic groups are O, N, S, P, Se, T
e is a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one heteroatom in the ring, and has a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group,
Nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), Representative examples include 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazole-
1-yl, 5-methylthio-1,3,4-thiadiazol-2-yl and 5-methyl-1,3,4-oxadiazol-2-yl.

Preferred examples of the substituent in the cyan coupler of the formula (II) of the present invention will be described below. Preferably -CONR ₄ R ₅ or -SO ₂ NR ₄ R ₅ is as R _1,
Specific examples include carbamoyl, Nn-butylcarbamoyl, Nn-dodecylcarbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N-cyclohexylcarbamoyl, N- [3- (2,4-di-t -Pentylphenoxy) propyl] carbamoyl, N-hexadecylcarbamoyl, N- [4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl, N- (3-
Dodecyloxy-2-methylpropyl) carbamoyl,
N- [3- (4-t-octylphenoxy) propyl]
Carbamoyl, N-hexadecyl-N-methylcarbamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N- [4- (2,4-di-t-pentylphenoxy) butyl] sulfamoyl. R ₁ is particularly preferably —CONR ₄ R ₅ .

R ₂ and k are most preferably k = 0, that is, unsubstituted, and then k = 1. R ₂ is preferably a halogen atom, an alkyl group (eg, methyl,
Isopropyl, t-butyl, cyclopentyl), a carbonamide group (for example, acetamido, pivalinamide, trifluoroacetamide, benzamide), a sulfonamide (for example, methanesulfonamide, toluenesulfonamide) or a cyano group.

R ₃ is preferably m in the formula (II-1)
= 0, and more preferably R ₇ is —COR ₈ [for example, formyl, acetyl, trifluoroacetyl, 2-ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4- (2,4-di-t-pentyl) Phenoxy) butanoyl], -COOR ₁₀ [eg, methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl, 2-methoxyethoxycarbonyl] or -SO ₂ R ₁₀ [eg, methylsulfonyl,
n-butylsulfonyl, n-hexadecylsulfonyl,
Phenylsulfonyl, p-tolylsulfonyl, p-chlorophenylsulfonyl, trifluoromethylsulfonyl], and particularly preferably, R ₇ is —COOR ₁₀ .

X is preferably a hydrogen atom, a halogen atom,
—OR ₁₁ [for example, ethoxy, 2-hydroxyethoxy,
2-methoxyethoxy, 2- (2-hydroxyethoxy) ethoxy, 2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N- (2-methoxyethyl) carbamoylmethoxy, 1-carboxytridecyloxy , 2
Alkoxy groups such as methanesulfonamidoethoxy, 2- (carboxymethylthio) ethoxy, 2- (1-carboxytridecylthio] ethoxy, for example 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t -Octylphenoxy, 4-nitrophenoxy, 4- (3-carboxypropanamide)
Aryloxy groups such as phenoxy, 4-acetamidophenoxy] or -SR ₁₁ [for example, carboxymethylthio, 2-carboxyethylthio, 2-methoxyethylthio, ethoxycarbonylmethylthio, 2,3-dihydroxypropylthio, 2- (N Alkylthio groups such as, for example, 4-carboxyphenylthio, 4-methoxyphenylthio,
Arylthio groups such as-(3-carboxypropanamido) phenylthio], and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an alkylthio group.

The coupler represented by the general formula (II) is a dimer or a multimer which is bonded to each other via a divalent or divalent or higher valent group at the substituent R ₁ , R ₂ , R ₃ or X. May be formed. In this case, the number of carbon atoms may be out of the range specified for each substituent. When the coupler represented by the general formula (II) forms a multimer, an addition-polymerizable ethylenically unsaturated compound having a cyan dye-forming coupler residue (a homo- or copolymer of a cyan-color-forming monomer is a typical example, Is the formula (II-
It is represented by 2). Formula (II-2) - (G i) gi - (H j) hj - group represented by the formula G _i is a repeating unit derived from the color forming monomer formula (II-2) (II- 3) in and, H _j is a repeating unit derived from the non-color forming monomer, i is a positive integer, j is 0 or represents a positive integer, respectively, the weight fraction of each gi and hi are G _i or H _j Represents Here when i or j is two or more, G _i or H _j represents contain repeating units of the plurality of types. Formula (II-3)

[0075]

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In the formula (II-3), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom.
Represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a divalent group having carbon atoms at both terminals such as a substituted or unsubstituted alkylene group, phenylene group, and oxydialkylene group. And L is-
CONH-, -NHCONH-, -NHCOO-, -N
HCO-, -OCONH-, -NH-, -COO-,-
OCO -, - CO -, - O -, - SO 2 -, - NHSO 2
— Or —SO ₂ NH—. a, b, and c represent an integer of 0 or 1. Q represents a cyan coupler residue obtained by removing one hydrogen atom from R ₁ , R ₂ , R ₃ or X of the compound represented by formula (II).

[0077] As the repeating not couple with the oxidation product of an aromatic primary amine developing agent to give a unit H _j non-color forming ethylenic monomer, acrylic acid, alpha-chloro acrylic acid, alpha-alkyl acrylic acid (Eg, methacrylic acid), amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, 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 Acrylates and β-hydroxyethyl methacrylates), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives such as vinyl toluene, divinylbenzene, vinyl) Acetophenone and sulfostyrene), itaconic acid, citraconic acid,
There are crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine.

In particular, acrylic esters, methacrylic esters and maleic esters 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 vinyl monomer corresponding to the formula (II-3) is in the form of a copolymer to be formed, for example, a solid , Liquid, micellar and physical properties and / or chemicals such as solubility (solubility in water or organic solvents), compatibility of photographic colloid compositions with binders such as gelatin, its flexibility , Thermal stability, coupling reactivity with an oxidized developer, diffusion resistance in a photographic colloid, and the like can be selected. These copolymers may be random copolymers or copolymers having a specific sequence (eg, block copolymer, alternating copolymer).

The number average molecular weight of the cyan polymer coupler used in the present invention is usually on the order of several thousand to several million, but oligomeric polymer couplers having a molecular weight of 5,000 or less can also be used. The cyan polymer coupler used in the present invention is an organic solvent (eg, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate).
Even if it is a soluble lipophilic polymer, even if it is a hydrophilic polymer miscible with hydrocolloid such as gelatin aqueous solution,
Further, a polymer having a structure and properties capable of forming micelles in a hydrocolloid may be used.

In order to obtain a lipophilic polymer coupler soluble in an organic solvent, a lipophilic non-color-forming ethylene-like monomer (eg, acrylate, methacrylate, maleate, vinylbenzene, etc.) is mainly used as a copolymer component. It is preferable to select The general formula (II-
The lipophilic polymer coupler obtained by polymerization of a vinyl monomer to give a coupler unit represented by 3) may be prepared by dissolving an organic solvent in an organic solvent and emulsifying and dispersing it in the form of a latex in an aqueous gelatin solution, or directly. It may be made by an emulsion polymerization method.

The method of emulsifying and dispersing a lipophilic polymer coupler in latex form in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and the method of emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,080. 370,952
Can be used. Alternatively, to obtain a neutral or alkaline water-soluble hydrophilic polymer coupler, N- (1,1-dimethyl-2-sulfonatoethyl) acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate , Potassium styrenesulfinate, acrylamide,
It is preferable to use a hydrophilic non-color-forming ethylene-like monomer such as methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine or the like as a copolymer component.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and a water-miscible organic solvent such as lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide, and dimethylacetamide can be used. It can also be dissolved and added to a mixed solvent of water and water. Further, it may be added by dissolving in an aqueous alkali solution or an organic solvent containing alkaline water. Further, a small amount of a surfactant may be added.

The specific examples of each substituent in the formula (II) and the cyan coupler represented by the formula (II) are shown below.

Example of R ₁

[0086]

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[0087]

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Example of R ₂

[0089]

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Examples of R ₃ NH—

[0091]

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[0092]

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Example of X

[0094]

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[0095]

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Specific examples of the cyan coupler represented by the general formula (II)

[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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[0105]

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Other specific examples of the cyan coupler represented by the formula (II) and / or methods for synthesizing these compounds are described in, for example, US Pat. No. 4,690,889, and
-237448, 61-153640, 61-
145557, 63-208042, 64-3
1159 and West German Patent 3,823,049A. As described in JP-A-62-269958, the use of a small amount of a high-boiling organic solvent for dispersing the cyan coupler represented by the formula (II) can further improve sharpness and desilvering properties. Is preferred.

Specifically, a high-boiling organic solvent is used in a weight ratio of 0.3 or less, more preferably 0.1 or less, to the cyan coupler represented by the formula (II). The total amount of the cyan coupler represented by the formula (II) is at least 30 mol%, preferably at least 50 mol%, more preferably at least 70%, even more preferably at least 90 mol% of all the cyan couplers.
Mol% or more. The cyan coupler represented by the formula (II) is preferably used in combination of two or more kinds. When the same color sensitivity is divided into two or more layers having different sensitivities, a 2-equivalent cyan coupler is added to the highest sensitivity layer. It is preferable to use a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use one or both of them in the same color-sensitive layer other than the above.

Next, the phenolic cyan coupler represented by the general formula (III) will be described in detail below. In the general formula (III), R ₁ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 36 (preferably 4 to 30) carbon atoms,
An optionally substituted aryl group having 6 to 36 C atoms (preferably 12 to 30) or 2 to 36 C atoms (preferably 1 to 30)
2-30) represents a heterocyclic group. Here, the heterocyclic group is a 5- to 7-membered optionally condensed heterocyclic group having at least one heteroatom selected from N, O, S, P, Se, and Te in the ring. As 2-furyl, 2-phenyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl,
Examples include 2-imidazolyl and 4-quinolyl. Examples of the substituent of R ₁ include a halogen atom, a cyano group, a nitro group,
Carboxyl group, sulfo group, alkyl group, aryl group,
Heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, imide group, amino Group, ureido group, alkoxylcarbonylamino group or sulfamoylamino group (hereinafter referred to as substituent group A), and the like,
Preferred examples of the substituent include an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group and an imide group.

In the general formula (III), R ₂ has a C number of 6 to 36.
(Preferably 6 to 15) aryl groups, which may be substituted with a substituent selected from the aforementioned substituent group A or may be a condensed ring. Here, preferable substituents include a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (eg, acetyl, benzoyl), and an alkyl group (eg, methyl, t-butyl, trifluoromethyl, trichloro). Methyl), alkoxy groups (eg, methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl groups (eg, methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (eg, phenylsulfonyl, p-tolylsulfonyl, p -Chlorophenylsulfonyl), an alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), a sulfonamide group (eg, methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), Bamoiru group (e.g. N, N- dimethylcarbamoyl, N- phenylcarbamoyl), or a sulfamoyl group (e.g. N, N
-Diethylsulfamoyl, N-phenylsulfamoyl). R ₂ is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4-cyano group. Phenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy- 4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4- Trifluoromethylphenyl or 3-sulfone A Dofeniru, particularly preferably 4-cyanophenyl, 3-cyano -
4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (III), Z represents a hydrogen atom or a coupling-off group which can be removed by a coupling reaction with an oxidized aromatic primary amine developing agent. Examples of the coupling-off group include a halogen atom, a sulfo group,
An alkoxy group having 1 to 36 (preferably 1 to 24) C atoms;
An aryloxy group having 6 to 36 (preferably 6 to 24) C atoms, an acyloxy group having 2 to 36 (preferably 2 to 24) C atoms, an alkylsulfonyl group having 1 to 36 (preferably 1 to 24) C atoms, An arylsulfonyl group having 6 to 36 C atoms (preferably 6 to 24),
24) an alkylthio group having 6 to 36 C atoms (preferably 6
To 24), a heterocyclic thio group having 1 to 36 (preferably 2 to 24) C atoms (for example, 2-benzothiazolylthio, 2,4-diphenoxy-1,3,5-triazole-6-thio) , 2-pyridylthio, tetrazolylthio, 2-thiazolylthio), an imide group having 4 to 36 (preferably 4 to 24) C atoms, 1 to 36 (preferably 1 to 36)
24) a carbamoyloxy group or a heterocyclic group bonded to a coupling active site by a nitrogen atom having 1 to 36 (preferably 2 to 24) carbon atoms (eg, pyrazolyl, imidazolyl,
1,2,4-triazol-1-yl, tetrazolyl)
There is. Here, the group below the alkoxy group is the substituent group A
May be substituted by a substituent selected from Z is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group, or an aryloxy group.

Specific examples of R ₁ , R ₂ and Z in formula (III) are shown below.

Examples of R ₁

[0113]

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[0114]

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[0115]

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Examples of R ₂

[0117]

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Example of Z

[0119]

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[0120]

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Specific examples of the cyan coupler represented by the general formula (III) are shown below. However, A to Z and a to f are
It is a serial number of a specific example of R ₁ in Chemical formulas 2 and 3.

[0122]

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[0123]

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[0124]

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[0125]

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Cyan couplers represented by the general formula (III) are described in, for example, JP-A-56-65134 and JP-A-61-2775.
Nos. 63-159848 and 63-161450
No. 63-161451, JP-A-1-254956
And U.S. Pat. No. 4,923,791.

The cyan coupler represented by formula (II) or (III) in the present invention is generally used in an amount of 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻ mol per mol of silver halide in the layer to be used. It can be used in the range of ³ mol to 8 × 10 ^-1 mol. In the present invention, more preferably, the compound represented by the general formula (II)
Is a cyan coupler represented by

Next, the compound of the formula [M] according to the present invention will be described in detail.

Of the coupler skeletons represented by the general formula [M] used in the present invention, preferred are 1H-imidazo [1,2-b] pyrazole and 1H-pyrazolo [1,5
-B] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H
-Pyrazolo [1,5-d] tetrazole, each represented by the formulas [MI], [M-II],
It is represented by [M-III] and [M-IV].

More preferred are compounds represented by the formula [M-II].

[0131]

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In these formulas, the substituents R ₁₁ , R ₁₂ , R
₁₃ and X will be described in detail. R ₁₁ is a hydrogen atom,
Halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy 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, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group , A sulfinyl group, a phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁₁ is a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an alkyl group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms,
Aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, 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), an aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic ring Groups (eg, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxyl, amino, alkoxy (eg, methoxy, ethoxy, 2-methoxyethoxy, 2- Dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy,
-Methoxycarbamoylphenoxy), an acylamino group (e.g., acetamido, benzamide, tetradecanamido, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, -{4- (4-hydroxyphenylsulfonyl) phenoxy} decaneamide), 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- {α-
(3-t-butyl-4-hydroxyphenoxy) dodecanamido @ anilino), a ureido group (for example, phenylureide, methylureide, N, N-dibutylureide), a sulfamoylamino group (for example, N, N-dipropylsulfur) Moylamino, 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, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p- Toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butylbenzenesulfonamide), 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 (Eg methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
A heterocyclic oxy group (for example, 1-phenyltetrazole-
5-oxy, 2-tetrahydropyranyloxy), an 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), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg, phenoxycarbonylamino), imide group (eg, N-succinimide, N-phthalimido, 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, phenoxyphosphonyl) Octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), or an azolyl group (eg, imidazolyl, pyrazolyl) , 3-chloro-
Pyrazol-1-yl, triazole).

Among these substituents, the group which can have a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁₁ includes an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, and an acylamino group. Can be.

R ₁₂ has the same meaning as the substituent described for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group. And a cyano group.

R ₁₃ is the same as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group,
An aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, and an acyl group, and more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, and an arylthio group. Group.

X represents a hydrogen atom or a group which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent.
An alkoxy group, an aryloxy group, an acyloxy group, an alkyl or arylsulfonyloxy group, an acylamino group, an alkyl or arylsulfonamide group,
An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl, aryl or heterocyclic thio group, a carbamoylamino 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 groups permitted as substituents for R ₁₁ .

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, methylsulfonylethoxy, ethoxycarbonylmethoxy), an aryloxy group (for example, 4-methylphenoxy, 4-chloro) Phenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy,
3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), acylamino group (for example, dichloro) Acetylamino, heptafluorobutyrylamino), an alkyl or aryl sulfonamide group (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), Aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (eg, Decylthio, 1-carboxy-dodecyl thio, phenylthio, 2-butoxy -5-t
-Octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazole, 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 may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or ketone as a leaving group bonded via a carbon atom in addition to these. X may contain a photographically useful group such as a development inhibitor and a development accelerator. Preferred X is a halogen atom,
It is an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to a coupling active site with a nitrogen atom.

Examples of the compound of the magenta coupler represented by the general formula [M] are shown below, but the present invention is not limited thereto.

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

References describing a method for synthesizing the coupler represented by the general formula [M] are listed below. The formula [M−
Compounds of the formula I] include, for example, U.S. Pat. No. 4,500,630,
The compound of formula [M-II] is disclosed in U.S. Pat. No. 4,540,654.
No. 4,705,863, JP-A-61-65245.
Nos. 62-209457 and 62-249155, the compounds of the formula [M-III] are disclosed in JP-B-47-2741.
No. 1, U.S. Pat. No. 3,725,067, etc.
The compound [IV] can be synthesized by the method described in JP-A-60-33552.

The magenta coupler represented by the general formula [M] of the present invention is added to the green-sensitive emulsion layer, and the total amount thereof is 0.01 to 1.0 g / m ² , preferably 0.0 to 1.0 g / m ² .
5~0.8g / m ^2, more preferably 0.1~0.5g
/ M ² . The method of adding the magenta coupler of the present invention to the light-sensitive material is according to the method of other couplers described below,
The amount of the high-boiling organic solvent used as the dispersing solvent is from 0 to 4.0, preferably from 0 to 2.0, more preferably from 0.1 to 2.0, as a weight ratio based on all couplers added to the magenta coupler-containing layer. 1.5, more preferably 0.1.
3 to 1.0.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue color-sensitive layer are provided in this order.
However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-43748, JP-A-59-1
13438, 59-113440, 61-20037, 61-20038
Or a DIR compound as described in JP-A No. 2000-205, and may contain a color mixing inhibitor as usually used. The plurality of silver halide emulsion layers constituting each unit light-sensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition,
57-112751, 62-200350, 62-206541, 62
As described in JP-A-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support. As a specific example, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) /
High sensitivity red photosensitive layer (RH) / low sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL
/ GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. JP-A-56-25738, 62-6
As described in Japanese Patent No. 3936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer,
The middle layer is provided with a silver halide emulsion layer having a lower sensitivity, and the lower layer is provided with a silver halide emulsion layer having a lower sensitivity than that of the middle layer. An arrangement composed of three layers is exemplified. Even when such three layers having different sensitivities are used, as described in JP-A-59-202464, a medium-sensitivity emulsion layer is disposed in a layer having the same color sensitivity from the side away from the support. It may be arranged in the order of / high-speed emulsion layer / low-speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, U.S. Patent Nos. 4,663,271 and 4,705,744
Nos. 4,707,436 and JP-A-62-160448, 63-89850
It is preferable to dispose a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the publication of JP-A No. 163/1972, adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or iodochloroiodide containing about 2 to 15 mol% of silver iodide. It is silver halide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions which can be used in the present invention are described, for example, in Research Disclosure (RD) No. 17643 (December 1978).
Mon), pp. 22-23, "I. Emulsion preparation
and types) ”and No. 18716 (November 1979), 648
No. 307105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chimie et Physique Photographique,
Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin,
Published by Focal Press (GF Duffin, Photographic E
mulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VL Zelikman et al., Making and Coating Photog).
raphic Emulsion, Focal Press, 1964).

The monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
No. 48, 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion.
They can be mixed and used in the same layer. U.S. Patent No.
No. 4,082,553, silver halide grains having a fogged surface, U.S. Pat.No. 4,626,498, silver halide grains having a fogged interior described in JP-A-59-214852, and photosensitive silver halide It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat.
No. 9-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged may have the same halogen composition or different halogen compositions. Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is
It is preferably from 0.01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but may be monodispersed (at least 95% of the weight or number of silver halide grains is ± 40% of the average grain size). %).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives which can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, page 866-868 Strong Color sensitizer 〜Page 649 right column 4. Brightener 24 page 647 page right column 868 5. Fogging prevention page 24-25 page 649 right column 868-870 agent, stabilizer 6.Light absorber, 25- Page 26 649 Right column Page 873 Filter 〜Page 650 Left column Dye, UV absorber 7.Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image 25 Page 650 Page Left column 872 Stabilizer 9. Hardener page 26 page 651 left column 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizer, page 27 page 650 right column page 876 Lubricant 12. Coating aid Pp. 26-27 650 right column 875-876 Surfactant 13. Static 27 page 650 right column 876-877 Inhibitor 14. Matsuto 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,987 and US Pat.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in 4,435,503 to the photosensitive material. U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A 1-2835
It is preferable to include the mercapto compound described in No. 51. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained. In the light-sensitive material of the present invention, WO 88/04794, dyes dispersed by the method described in JP-A-1-502912 or European Patent No. 317,308A, U.S. Patent No. 4,420,555, JP-A-1-259358 It is preferable to include the dye described in (1). Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure Nos. 17643 and VII-CG and VII-CG and Nos. 307105 and VII-C.
-G are described in the patents. As yellow couplers, for example, U.S. Pat.
22,620, 4,326,024, 4,401,752, 4,24
No. 8,961, No. 58-10739, UK Patent No. 1,425,020
Nos. 1,476,760; U.S. Pat.Nos. 3,973,968, 4,3
14,023, 4,511,649, European Patent No. 249,473A,
And the like are preferred.

As magenta couplers which can be used in combination with the magenta coupler of the present invention, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat. No. 4,310,619
No. 4,351,897, European Patent No. 73,636, U.S. Patent No.
Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552,
Research Disclosure No.24230 (June 1984
Mon), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730
Nos. 55-118034, 60-185951, U.S. Pat.
00,630, 4,540,654, 4,556,630, international publication
Those described in WO88 / 04795 and the like are particularly preferred. As the cyan coupler that can be used in combination with the cyan coupler of the present invention,
Phenolic and naphthol couplers,
U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,2
No. 33, No. 4,296,200, No. 2,369,929, No. 2,801,171
Nos. 2,772,162, 2,895,826, 3,772,002
Nos. 3,758,308, 4,334,011, 4,327,173
No., West German Patent Publication No. 3,329,729, European Patent No. 121,365A
No. 249,453A, U.S. Pat.Nos. 3,446,622, 4,33
No. 3,999, No. 4,775,616, No. 4,451,559, No. 4,427,7
No. 67, No. 4,690,889, No. 4,254,212, No. 4,296,199
And those described in JP-A-61-42658 are preferred. Furthermore, JP-A Nos. 64-553, 64-554, 64-555, 64-5
A pyrazoloazole coupler described in No. 56 and an imidazole coupler described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211.
Nos. 4,367,282, 4,409,320, 4,576,910
No. 2,102,137, European Patent No. 341,188A and the like.

As couplers in which a coloring dye has an appropriate diffusibility, US Pat. No. 4,366,237 and British Patent No. 2,12
No. 5,570, European Patent No. 96,570, German Patent (public) No. 3,
Those described in No. 234,533 are preferred. Colored couplers to correct unwanted absorption of coloring dyes
Disclosure No. 17643, Sections VII-G, No. 30710
5, VII-G, U.S. Pat.No. 4,163,670, JP-B-57-3
No. 9413, U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent No. 1,146,368 are preferred. Also,
U.S. Pat.No. 4,774,181 describes a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a dye precursor group that can form a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the aforementioned RD Nos. 17643, VII-F and 307105, VII-F.
57-151944, 57-154234, 60-184248, 63
-37346, 63-37350, U.S. Pat.No. 4,248,962,
Those described in 4,782,012 are preferred. RD No.11
The bleaching accelerator releasing couplers described in 449, No. 24241, JP-A-61-201247, etc. are effective for shortening the time of the processing step having bleaching ability, The effect is great when added to a photosensitive material using silver particles. Couplers which release a nucleating agent or development accelerator imagewise during development are described in GB 2,097,1
No. 40, No. 2,131,188, JP-A-59-157638, No. 59-170
Those described in No. 840 are preferred. In addition, JP-A-60-10702
No. 9, 60-252340, JP-A-1-44940, 1-45687
The redox reaction with the oxidized form of the developing agent described in No.
Compounds that release fogging agents, development accelerators, silver halide solvents and the like are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and the like, and US Pat. Nos. 4,283,472 and 4,33.
No. 8,393, multi-equivalent coupler described in 4,310,618, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950, JP-A-62-24252 and the like.
IR redox releasing redox compounds, EP 173,
Nos. 302A and 313,308A, couplers releasing dyes that recolor after release, ligand releasing couplers described in U.S. Pat.No. 4,555,477, and couplers releasing leuco dyes described in JP-A-63-75747. And couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate) (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Esters of isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, dichloropropyl
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylase) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, the boiling point is about 30 ℃ or more, preferably 50 ℃
An organic solvent having a temperature of about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747, JP-A-62-272248,
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- ( It is preferable to add various preservatives or fungicides such as 4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the aforementioned R
D. No. 17643, page 28, No. 18716, page 647, right column, 648
No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering (Photogr. S) by A. Green et al.
ci. & Eng.), 19 Certificates, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 90% of the maximum swollen film thickness reached when the treatment is performed for 15 minutes is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness. Film swelling speed T
_{The 1/2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness. The light-sensitive material of the present invention preferably has a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of this back layer is 150 ~
500% is preferred.

The support of the color negative film used in the present invention is described in WO 90/04205,
FIG. Those having the magnetic recording layer described in 1A are preferable. As described in JP-A-4-62543, the support having such a magnetic recording layer preferably has a conductive layer containing zinc, titanium, tin or the like on one surface. Further, those having a stripe magnetic recording layer described in JP-A-4-124628 and having a transparent magnetic recording layer adjacent to the stripe magnetic recording layer can also be used. A protective layer described in JP-A-4-73737 can be provided on the magnetic recording layer.

The thickness of the support is preferably from 70 to 130 μm, particularly preferably from 80 to 120 μm. As the material for the support, various plastic films described in JP-A-4-124636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used. Preferred examples include cellulose derivatives (for example, diacetyl). -, Triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate) and polyesters described in JP-B-48-40414 (for example, polyethylene terephthalate, poly-1,4-).
Cyclohexane dimethylene terephthalate, polyethylene naphthalate). The film support used in the present invention has a higher draining effect and can reduce the incorporation of the prebath component into the next step. Therefore, polyethylene terephthalate or a functional material, February, 1991, February,
Polyethylene naphthalate described on pages 20 to 28 is preferred.

The package (patrone) for accommodating the color negative film of the present invention may be any of those currently used or known, and in particular, US Pat. No. 4,834,30.
No. 6, FIG. 1 to FIG. 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. FIG. Those described in No. 3 are preferred.

The format of the color negative film used in the present invention is based on Japanese Industrial Standard "JIS.K-7519".
(1982) ", any known one can be used. However, the format having a small number of perforations and a narrow width described in Japanese Patent Application Laid-Open No. 4-287040 has a small processing liquid take-out and low replenishment. It is preferable because it is suitable for rapid processing. In processing a film having such a format, it is preferable to use a jet stirring method in which a jet of a processing liquid collides with a film surface.

[0168]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Samples 101, which are multilayer color photosensitive materials, were prepared by applying each layer having the composition shown below in multiple layers. (Composition of photosensitive layer) The main materials used for each layer are classified as follows. ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component is a coating expressed in g / m ^2. In the case of silver halide, the coating amount is expressed in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) 2,5-di-t-pentadecyl hydroquinone 0.18 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 gelatin 1.08

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.12 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.080 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-20 .023 HBS-1 0.10 gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.044 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10.

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion C 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

Tenth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion C silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-30 .50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Medium Speed Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth Layer (High Sensitive Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-10 .070 Gelatin 0.86

Fourteenth layer (first protective layer) Silver iodobromide emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-30 .10 S-1 0.20 gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-3, B-4 to B -6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium and rhodium salts. Table 1 shows the properties of the emulsion used in each emulsion layer.

[0185]

[Table 1]

In Table 1, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope. The chemical formulas and the like of the compounds used for each layer are shown below.

[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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The sum of the weights of the coupler and the high boiling point organic solvent in the fourth to fifteenth layers of the sample 101 was 5.168.
mg / m ² . This is because the Ex from the 4th layer to the 15th layer
It is calculated as the sum of the coating amounts (g) per m ² of the material described in C, ExM, ExY, and HBS.

The samples 102 to 106 are the seventh
Each coating amount from the layer to the 15th layer is indicated by ×
2.0, × 1.8, × 1.5, × 0.8, and × 0.5. The fourth in parentheses of the sample in Table-A
The sum of the weight of the coupler and the high boiling point organic solvent from the layer to the fifteenth layer is shown.

These samples were exposed imagewise with red light,
The processing was performed using an automatic developing machine until the replenishment amount of the color developing solution was three times the volume of the tank. The processing steps and the composition of the processing solution are shown below.

[0205] * The replenishment amount is 35 mm of photosensitive material and 1.1 m width (24E
x. The stabilizing solution is a countercurrent system from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. For replenishment to the bleach-fixing bath, a cut is provided at the top of the bleaching tank and the fixing tank of the automatic processor, and all the overflow liquid generated by supplying the replenisher to the bleaching tank and the fixing tank is transferred to the bleach-fixing bath. It was made to flow in. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the bleach-fixing step, the amount of the bleach-fixing liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm width of the photosensitive material. 2.5 ml, 2.0 ml, 2.0 ml, 2.0 ml
Milliliters. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline (P-5) sulfate (developer) 4.5 6.0 1.0 liter with water 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15

(Bleaching solution) Tank solution (g) Replenisher (g) Ferric ammonium 1,3-diaminopropanetetraacetate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Water 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia) 4.4 4.4

(Bleach-fixing tank solution) A mixture of the above-mentioned bleaching tank solution and the following fixing tank solution in a ratio of 15 to 85 (volume ratio). (PH 7.0)

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium sulfite 1957 Ammonium thiosulfate aqueous solution (700 g / L) 280 mL 840 mL Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Add water 1.0 L 1.0 L pH (Adjusted with ammonia water and acetic acid) 7.4 7.45

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 mg /
It was treated to less than 1 liter, followed by the addition of 20 mg / l sodium diisocyanurate and 150 mg / l sodium sulfate. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2-Benzoisothiazolin-3-one 0.03 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water 1.0 liter pH 8.5

Further, the same treatment was performed by changing the developing agent P-5 in the color developing solution to an equimolar amount to each of the developing agents shown in Table-A. After the processing, the characteristics of the light-sensitive material were measured with red light. In Experiments A01 and A08 to A12 of Table-A, when the R concentration when the sample 101 was processed with the developing agent P-5 was 1.0. The R density with respect to the exposure amount was determined.
Similarly, in Experiment Nos. A02 and A03, sample 102,
In experiment Nos. A04 and A05, sample 103, experiment no.
In A06 and A07, Sample 104, Experiment No. A13-
In A16, the sample 105 was processed, and in Experiments A17 to A21, the sample 106 was processed with the developing agent P-5. The results are shown in Table-A.

[0213]

[Table 2]

As apparent from Table A, the total weight of the couplers and the high boiling point organic solvents in the fourth to fifteenth layers was 1
When it is 10 to 10 mg / m ² , high R concentration (1.0 or more) can be obtained by processing with the developing agent of the present invention. This is because the coupler and the high boiling organic solvent in the upper layer
If it is 10 to 10 mg / m ² , it indicates that the developing agent of the present invention does not become diffusion-controlled, and the lower layer is developed in a shorter time than before.

Example 2 In the sample 101 prepared in Example 1, Table-B (Table 3
As shown in Table 4), the cyan dye-forming couplers of the third, fourth, and fifth layers and the magenta dye-forming couplers of the seventh, eighth, and ninth layers were changed in equimolar amounts. ~ 2
No. 12 was formed.

[0216]

[Table 3]

[0219]

[Table 4]

[0218]

Embedded image

These samples were subjected to imagewise exposure with white light, and processed in the same manner as in Example 1. At this time, the developing agents were changed in equimolar amounts as shown in Table-C, and the color development time was further changed from 1 minute 15 seconds to 4 minutes 15 seconds.
Processing was performed by shaking every second.

In Table C, Sample 101 was treated with a developing agent P-5.
When the color development time is 3 minutes and 15 seconds, the yellow (B) density, magenta (G) density, and cyan (R) density are 2.3, 2.0, and 1.5, respectively. The color development time to obtain the same color density at the same exposure amount is 3
The difference (second) from the minute 15 seconds was shown. In other words, the larger the value is, the shorter the processing time is.
The smaller the difference between B, G, and R values, the better the color balance.

[0221]

[Table 5]

As is clear from Table-C, when the red-sensitive emulsion layer contains the cyan dye-forming coupler of the present invention, the rapidity of R density and the color balance are improved. When the green-sensitive emulsion layer contains the magenta dye-forming coupler of the present invention, the rapidity of R concentration is improved. This is presumably because the amount of the developing agent of the present invention incorporated into the oil-soluble phase containing the magenta coupler of the present invention is reduced. Further, when the sample containing the cyan dye-forming coupler of the present invention in the red-sensitive emulsion layer and the magenta dye-forming coupler of the present invention in the green-sensitive emulsion layer is processed with the developing agent of the present invention, the fastest processing and color Excellent balance. In addition, two of the cyan dye-forming couplers of the present invention
The equivalent is particularly effective.

Example 3 The sample 101 prepared as described above was subjected to imagewise exposure, and was continuously processed with the following processing solution until the replenishment amount of the bleach-fixing solution became 10 times the tank capacity. The bleach-fix solution was subjected to silver recovery in-line with a silver recovery device, and the solution after silver recovery was subjected to a regeneration treatment and reused as a replenisher for the bleach-fix solution. As a silver recovery apparatus, a small electrolytic silver recovery apparatus having a carbon anode and a stainless steel cathode was used, and the current density was 0.5 A / dm ² . FIG. 1 shows a schematic diagram of a silver recovery system.

In FIG. 1, the overflow of the bleach-fixing solution is directly connected to the silver recovery device, and the solution after the electrolytic treatment is returned to the original bleach-fixing tank through the filter by the pump 1.
The Orobar flow from the silver recovery device collects 600 ml per 1 liter of overflow liquid into a regeneration tank, and when the amount of recovery reaches 1 liter, blows air for about 2 hours, then adds a regenerant and bleaches with the pump 2. It is sent to the fixer replenishment tank. The remaining liquid was discharged, and was separately discharged after collecting silver. The waste liquid amount was 196 ml per 1 m ² of the sample 101. In the water washing treatment, a countercurrent cascade was performed using a five-stage multi-room water washing tank arranged horizontally. The overflow of the first washing water was cascaded to the bleach-fix bath of the previous bath. Between the fourth and fifth rinsing,
A reverse osmosis device RC30 (manufactured by FUJIFILM Corporation) was installed. The processing steps are described below. FIG. 2 is a schematic diagram of the processing machine.

[0225]

In FIG. 2, CD is a color developing tank, Bl
ix indicates a bleach-fixing tank, W1 to W5 indicate first to fifth washing tanks, and RO indicates a reverse osmosis device. The broken line indicates the path of the photosensitive material. The numerical values (ml) in FIG. 2 are the replenishment amount (ml) and the waste liquid amount (ml) per 1 m ² of the photosensitive material. The crossover time from the color development to the bleach-fix and from the bleach-fix to the first washing is 3 seconds. The average takeout amount per photosensitive material 1 m ² is 68 ml. Further, as described in JP-A-3-280042, the temperature and humidity of the outside air of the processing machine were detected by a thermo-hygrometer, and the amount of evaporation was calculated and corrected for each tank. As the water for evaporation correction, the above-mentioned ion-exchanged water for washing water was used.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 4.0 4.0 1-hydroxyethylidene 1,1-diphosphonic acid 2.7 3.0 Potassium hydroxide 3.0 4.5 Sodium sulfite 4.0 9.5 Sodium bicarbonate 1.8-Potassium carbonate 31.7 39.0 Potassium bromide 6.5-Potassium iodide 1.3 mg-Developing agent of the present invention (D-12) 48.0 mmol 77.0 mmol Add water 1.0 liter 1.0 liter pH 10.05 12.10

(Bleaching-fixing solution) Mother liquor at start (g) Replenishing solution (g) Fixing agent (compound-A) 1.8 mol 2.97 mol Ferric ammonium 1,3-propylenediaminetetraacetate monohydrate 144.0 237.6 bromide Ammonium 40.0 66.0 Ammonium nitrate 20.0 33.0 Add water 1.0 liter 1.0 liter pH (25 ℃) (adjusted with acetic acid and ammonium water) 4.5 4.4

[0229]

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(Bleach-fixing regenerating agent) Addition amount (g) per liter of recovered solution for regeneration 1,3-propylenediaminetetraacetic acid ferric ammonium monohydrate 93.6 Fixing agent (compound-A) 1.17 mol ammonium bromide 26 Ammonium nitrate 13

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 mg.
Per liter or less, followed by addition of 20 mg / l of sodium diisocyanurate and 150 mg / l of sodium sulfate. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2-Benzoisothiazolin-3-one 0.03 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water 1.0 liter pH 8.5

By executing the above-described processing system, the amount of waste liquid after treating the sample 101 with 100 m ² was 19.6 liters. This is based on the total amount of waste liquid (about 250 liters) in a conventional processing system, for example, a color negative processing CN-16FA system of Fujifilm Corporation.
This corresponds to about one-third, indicating that the amount of waste liquid has been significantly reduced.

When the samples 201 to 212 were processed in the same manner, even if the color development time was as short as 60 seconds, the same color density as that obtained in the experiment B01 could be obtained. As a result, a color image forming method having excellent color reproducibility was obtained.

[0235]

The method of processing the silver halide color photographic light-sensitive material of the present invention with the developing agent of the present invention provides a color image forming method which is rapid and excellent in color reproducibility. Further effects can be obtained by including the cyan and / or magenta dye-forming coupler of the present invention in the light-sensitive material.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a system for performing in-line silver recovery from a bleach-fix solution.

FIG. 2 is a schematic diagram of a processing machine used in Example 3.

[Explanation of symbols]

 CD Color developing tank Blix Bleaching and fixing tank W1 First washing tank W2 Second washing tank W3 Third washing tank W4 Fourth washing tank W5 Fifth washing tank RO Reverse osmosis device

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 7/388 G03C 7/388 (56) References JP-A-3-149548 (JP, A) JP-A-63-106655 (JP) JP-A-2-149844 (JP, A) JP-A-61-261740 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 7/413

Claims (3)

(57) [Claims] An all-color-sensitive silver halide emulsion having at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support. In a color image forming method in which a silver halide color photographic light-sensitive material having an average silver iodide content of a layer of from 2 to 20 mol% is color-developed with a developer, the light-sensitive material is closest to the support. The sum of the weight of the coupler and the high boiling point organic solvent contained in the entire hydrophilic colloid layer present farther from the support than the layer is 1 g / m ^{2 to} 10 g / m
m ² , wherein the developer contains at least one aromatic primary amine color developing agent represented by the following general formula (D). Embedded image In the formula (D), R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched hydroxyalkyl having 3 to 8 carbon atoms whose main chain has 3 to 8 carbon atoms. Represents a group. R ₂ has 3 to 8 carbon atoms in which the main chain has 3 to 8 carbon atoms.
Represents a straight-chain or branched unsubstituted alkylene group of 8 or a straight-chain or branched hydroxyalkylene group of 3 to 8 carbon atoms having a main chain of 3 to 8 carbon atoms. R ₃ is carbon number 1
Represents a to 4 linear or branched alkyl group or alkoxy <br/> sheet group. 2. The red-sensitive silver halide emulsion layer closest to the support contains at least one cyan dye-forming coupler represented by the following general formula (II) or (III). 2. The color image forming method according to 1. Embedded image In the formula (II), R ₁ represents —CONR ₄ R ₅ , —SO ₂ NR ₄ R ₅ ,
_{-NHCOR 4, -NHCOOR 6, -NHSO 2} R 6, -
NHCONR ₄ R ₅ or —NHSO ₂ NR ₄ R ₅ , R ₂ is a group that can be substituted on a naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, X is a hydrogen atom or an aromatic group. And a group capable of leaving by a coupling reaction with an oxidized primary amine developer. However, R ₄ and R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₆ represents an alkyl group,
Represents an aryl group or a heterocyclic group. When k is plural, R ₂ may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may combine with each other to form a ring. R ₁ , R ₂ ,
A dimer or higher multimer linked to each other via a divalent or divalent or higher valent group in R ₃ or X may be formed. Embedded image In the formula (III), R ₁ represents an alkyl group , an aryl group or a heterocyclic group, R ₂ represents an aryl group, and Z represents a hydrogen atom or a coupling-off group. 3. A magenta dye represented by the following general formula [M] in at least one green-sensitive silver halide emulsion layer present farther from the support than the red-sensitive silver halide emulsion layer closest to the support. 3. The color image forming method according to claim 1, wherein at least one type of forming coupler is contained. Embedded image In the formula [M], R ₁ represents a hydrogen atom or a substituent.
Z represents a group of nonmetal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent.