JPS6346460A - Image forming method - Google Patents

Abstract

PURPOSE:To reduce the rinse time of a photosensitive material and to improve image storage stability by incorporating a specified magenta coupler, specifying the swelling degree of a photographic layer, and rinsing it. CONSTITUTION:The silver halide photosensitive material contains one of the magenta couplers represented by formula I and II is which R1 is H or a substituent; X is H or a group to be released by the coupling reaction with the oxidation product of an aromatic primary amine color developing agent; each of Za, Zb, and Zc is methine, =N-, or -N-; one of Za-Zb and Zb-Zc is a double bond, and the other is a single bond; W is aryl; Z is alkyl, aryl, or a heterocyclic group; and Y is acylamino, ureido, or anilino. The photographic layer of the photosensitive material has a swelling degree of 1.5-4.0, the total rinse time is controlled to 30-90sec, and the rinse water is replenished in an amount of 0.5-50 times the amount brought from the preceding step per unit area of the photosensitive material, thus permitting the photosensitive material having the specified magenta coupler to be rinsed in a short time with a saved amount of water, and staining to be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an image forming method, and more specifically to a method for forming a silver oxide color photographic material, in which the image storage stability is not impaired even if the washing treatment time is shortened. The image is related to the method of formation.

(Prior Art) Many studies have been conducted on shortening the processing time of silver halide color photographic materials. For example, methods for shortening the development time include increasing the temperature and pH of the developer retaining solution and using a development accelerator. Furthermore, methods of adding various accelerators are known as methods for shortening the desilvering process.

In order to shorten the processing time, it is effective to shorten the water washing process in addition to shortening the development process and desilvering process described above. Conventionally, the water washing treatment time was generally 2 to 3 minutes.

By the way, when the water washing process is shortened, it is inevitable that the bleaching components and fixing components will be insufficiently washed. In this case, the image storage stability of the processed photosensitive material deteriorates. Conventionally, various antifading agents have been added to color photosensitive materials for the purpose of improving image storage stability (for example, U.S. Pat. Nos. 2,816,028, 3,457,079, and 36,989).
No. 09, No. 3764337, No. 3700455, etc.), these anti-fading agents also become ineffective if the water washing process time is less than 1 minute and 30 seconds. That is, if the iron complex present in the bleach solution or bleach-fix solution is insufficiently washed, the remaining iron complex reacts with the remaining coupler, resulting in a problem of increased yellow stain during dark storage.

In addition, in the case of long-term continuous processing, yellow and/or magenta colored stains, which are thought to be mainly caused by the oxides of the developing agent, adhere to the photosensitive material, but when the water washing processing time is shortened as described in the present invention, If it takes a long time, the above-mentioned deposits will not be washed sufficiently, and a new problem will arise as stain immediately after treatment.

On the other hand, in the washing treatment process, significant water-saving treatment methods have been proposed in recent years with the main purpose of saving water resources and eliminating the need for washing piping when installing a treatment machine. Regarding these techniques, see Japanese Patent Application Laid-open Nos. 56-70549 and 57-132.
No. 146, No. 57-8543, No. 58-18631, No. 59-184343. No. 59-184345,
It is disclosed in No. 58-14834 and the like.

If the above-mentioned water-saving treatment is used and water washing is carried out for a short period of time as in the present invention, the cleaning effect in the washing process becomes more insufficient, and the problem of staining after the above-mentioned treatment and/or over time becomes even more serious. It turned out.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a developing process that shortens the washing process time, especially a processing method that does not impair image preservation even in long-term continuous processing and does not worsen staining immediately after processing. It is about providing.

A further object of the present invention is to provide a processing method that reduces the washing processing time and does not impair image storage stability or worsen staining immediately after processing even when water-saving processing is used. - (Means for solving the problem) The above object is a process in which the total processing time of the water washing process in the development processing of silver halide color photographic light-sensitive materials is shortened, such that the total processing time is 30 to 90 seconds. It has been found that this can be achieved by adjusting the degree of swelling of the photographic layer of the light-sensitive material to 1.5 to 4.0 in the process.

Furthermore, the above objective can be effectively achieved even when a so-called water saving process is carried out in which the amount of washing water replenished in the washing process is 0.5 to 50 times the amount brought in from the pre-bath of the color photographic light-sensitive material. Furthermore, the above tin chloride color photographic light-sensitive material has the following general formula (1) and general formula (II).
It has been found that the above object can be achieved more effectively when the composition contains at least one magenta coupler selected from the group of compounds.

The water washing treatment in the present invention includes not only the usual "water washing treatment" but also a simple treatment method in which no substantial water washing step is provided and only a so-called "stabilization treatment" is performed instead. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above.

The washing treatment time in the present invention is from 30 seconds to 1 minute and 30 seconds, preferably from 40 seconds to 1 minute and 10 seconds. The "washing processing time" herein refers to the time from when the photosensitive material comes into contact with the washing water until it reaches the drying zone, which is the final step. If the washing process is a multi-stage countercurrent washing process with two or more tanks, it represents the total washing time from contact with the washing water in the first tank until reaching the drying zone. The above definition also applies when a so-called 1 stabilization treatment is performed instead of ordinary water washing.If the water washing time is less than 30 seconds, the swelling degree of the photographic layer is within the range of the present invention. The yellow stain becomes high immediately and after a period of time, which is not preferable.

Another object of the present invention is to perform processing in a shortened water washing time of 1 minute and 30 seconds or less.

In order to shorten the washing process, the amount of washing water and the washing temperature are also important from a practical standpoint. It is difficult to specify the amount of water for washing in a normal "washing process" because it varies depending on the number of baths in the multistage countercurrent washing and the amount of pre-bath components brought into the photosensitive material. It is sufficient if the pre-bath component of the step is I×10 or less. In this specification, “
The prebath is generally a fixer or a bleach-fixer, but is not limited thereto. For example, in the case of three-tank countercurrent water washing, it is preferable to use about 1,000 rtt1 or more per meter of photosensitive material, preferably 5,000 mJ or more.

The washing process is a washing process using so-called water saving treatment, for example 2
It is preferable to use multistage countercurrent washing with more than one tank (for example, 2 to 9 tanks) to save washing water. Furthermore, it is more preferable to carry out a multistage countercurrent stabilization treatment process (so-called stabilization treatment) as described in JP-A-57-8543 instead of the usual water washing process. In this case, the pre-washing bath components of the final bath are preferably 5 x 10-2 or less. In the case of these water-saving treatments or stabilization treatments, the amount of washing water or stabilizing solution to be refilled is equal to 0 of the amount of "pre-bath" brought in per unit area of the photosensitive material.
．． It is preferably 5 to 50 times (depending on capacity), more preferably 3 to 30 times.

Various compounds can be used in the water washing and stabilization steps in the present invention for various purposes. For example, it is known to add bactericidal agents and anti-piping agents to prevent the growth of various bacteria, molds, and algae. For example, Shahnal of Antibacterial and
Antiba
ct, Antifung.

Agents) vol, 11s A5s p
207-223 (1983) and the compounds described in "The Chemistry of Antibacterial and Antifungal" by Hiroshi Hori, or JP-A-57-8543, JP-A-57-58143, JP-A-57 -97530, JP-A-58-105145, JP-A-58-134636, JP-A-59-→1440.1
26533, JP-A-59-184344, JP-A-59-
185336, JP-A-60-239750, JP-A-60
-239751, JP-A-60-247241, JP-A-6
0-260952, JP-A-61-2149, JP-A-61
-28947, Japanese Unexamined Patent Publication No. 61-28945, Patent Application No. 59-
158475, and the compounds and methods for their use described in the specifications of Japanese Patent Application No. 105487/1987 can be applied. In particular, inthiazolone derivatives (2-octyl-4-inthiazolin-3-one, 5-chloro0-2-methyl-4-inthiazolin-3-one, etc.), sulfanilamide derivatives (
sulfanilamido), 2 and benzotriazole derivatives (benzotriazole), 5-,'thirupene I
azole, 5-rolupenzothiazole, etc.)
is useful. In order to improve image stability after processing,
It is known to add various chelating agents. For example, inorganic phosphoric acid, organic carboxylic acid, aminopolycarboxylic acid, and organic phosphonic acid are useful;
No. 4, JP-A-58-134636, JP-A-59-12
No. 6533, JP-A-59-184343, JP-A-59
-184344, JP 59-184345, JP 59-185336, JP 60-135942, JP 60-238832, JP 60-2397
No. 48, JP-A-60-239749, JP-A-60-2
No. 39750, JP-A-60-239751, JP-A-6
0-242458, JP 60-262161, JP 61-4047, JP 61-4050, JP 61-4051, JP 61-4052, JP 61- 4053, JP-A-61-4054, JP-A-61-28942, JP-A-61-28945, and the compounds and methods of use described in the specifications thereof can be applied. especially,
Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene 1,1'
-diphosphonic acid, ethylenediamine-NNN'N'-tetramethylphosphonic acid, nitrilo-pre-trimethylenephosphonic acid are useful. Further, two or more of these chelating agents may be used in combination.

Metal compounds can also be used in combination with these chelating agents. For example, bismuth compounds (JP-A-58-1
34636), Bas Ca 5Ces Co
s In, L1% Mn, Ni, Pbs Ti5
Compounds of Sn s Zn SZr (Japanese Unexamined Patent Publication No. 59-18
No. 4344), Mg, Am Sr compound (JP-A No. 59
-185336) by force, especially BisCa
A compound of 5Mg5At is useful. Furthermore, in order to effectively proceed with water washing, a surfactant may be used (JP-A-57-197540), and a method of contacting with an ion exchange resin (JP-A-57-197540) for the purpose of removing components that have an adverse effect. 60-22'''0345), reverse osmosis treatment method (JP-A-60-241053), activated carbon,
Viscous substances, polyamide-based polymer compounds, polyurethane-based polymer compounds, phenol resins, epoxy resins, polymer compounds with hydranod groups, polymer compounds containing polytetrafluoroethylene, monohydric or polyhydric alcohols methacrylic acid mono Method of contacting ester-polyhydric alcohol with methacrylic acid polyester copolymer (JP-A-6
0-263151), electrodialysis treatment method (Japanese Unexamined Patent Publication No. 61-28949), etc. can be applied.

Furthermore, methods such as ultraviolet irradiation and passing through a magnetic field can also be applied to prevent the growth of bacteria and mold.

In case of further continuous processing, JP-A-60-233
No. 651, No. 60-235133, No. 60-2639
No. 41, No. 61-4048, No. 61-4049, No. 61-4055, No. 61-4056, No. 61-40
The methods of No. 57, No. 61-4058, and No. 61-4060 can be applied.

In addition to the above-mentioned additives, a fluorescent brightener, a hardening agent, etc. may be added to the water washing and stabilizing bath.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film conditioner after processing in order to improve image storage stability.

As for the various additives, two or more of the same or different desired compounds may be used in combination depending on the purpose.

The amount added should be the minimum amount necessary to achieve the purpose.
This is preferable from the viewpoint of the physical properties of the emulsion film (stickiness, etc.) of the photographic material after processing.

In order to increase the effect of washing out components in the membrane during water washing or stabilization treatment, it is preferable to circulate and stir the liquid.
In particular, a method that causes a strong liquid flow to flow on the surface of the light-sensitive material emulsion film (for example, gas stirring, liquid spraying, etc.) is preferred.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various gentle squeegees, nitrogen agitation, air agitation, etc., as necessary.

On the other hand, the photographic layer of the photographic material used in the present invention has a swelling degree of 1.5 to 4.0, preferably 2.0 to 3.5. The degree of swelling referred to herein refers to the value obtained by dividing the thickness of the photographic layer after immersing the photosensitive material in distilled water at 33° C. for 2 minutes by the thickness of the dry layer.

When the degree of swelling is less than 1.5, if the water washing treatment time is shortened (30 to 90 seconds) as in the present invention, the yellow stain will increase immediately after the treatment and after aging, which is not preferable.

Furthermore, if the degree of swelling is greater than 4.0, the yellow stain concentration is similarly undesirable. moreover,
If the degree of swelling is greater than 4.0, the mechanical strength of the photographic layer during the development process will decrease, causing failures such as the occurrence of scratches, and the amount of water absorbed will increase, resulting in a drying load, which is not preferable.

The photographic layer herein refers to a laminated hydrophilic colloid group layer that includes at least one photosensitive silver halide emulsion layer and is mutually permeable to water. It does not include a back layer provided on the opposite side of the photosensitive layer across the support. The photographic layer is usually formed from a plurality of layers involved in forming a photographic image, and includes, in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, and the like.

Any method may be used to adjust the swelling degree within the scope of the present invention, such as the amount and type of gelatin used in the photographic film, the amount and type of hardening agent, or drying after coating the photographic layer. It can be adjusted by changing the conditions and time-course conditions. Although it is advantageous to use gelatin in the photographic layer, other hydrophilic colloids can also be used. For example, gelatin derivatives, graft primers of gelatin and other polymers, albumin 1. Proteins such as casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, ? A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of remethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

Gelatin derivatives include gelatin and various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and dioxy compounds. The product obtained by reacting is used. Specific examples include U.S. Patent No. 2,614,928, U.S. Patent No. 3,132,945, U.S. Patent No. 3,186.8'46, U.S. Patent No. 3,312,553, British Patent No. 861,414, U.S. Patent No. 1,033 , No. 189, No. 1,005,784, and Japanese Patent Publication No. 42-26845.

The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. Particularly preferred are graft polymers with gelatin and polymers which are compatible to some extent with polymers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat. No. 2,763,625, U.S. Pat.
It is described in No. 2,956,884, etc. Typical synthetic hydrophilic polymer substances are, for example, West German patent applications (OLS
) 2,312,708, U.S. Patent No. 3.620,75
No. 1, No. 3,879,205, Special Publication No. 43-7561
It is stated in the number.

Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (tumethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2・,3--,
'Hydroxydioxane, etc.), activated vinyl compounds (1
, 3,5-triacryloyl-hexahydro-3-triazine, bis(vinylsulfonyl)methyl ether, N
.

N'-methylenebis-[β-(vinylsulfonyl)glopionamide], etc.), active rodene compounds (2,4
-dichloro-6-hydroxy-3-triazinato),
Mucohalogen acids (mucochloric acid, phenoxychloric acid, etc.) inoxazoles, dialdehyde starch,
2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Specific examples include U.S. Patent Nos. 1,870,354 and 2,080.
, No. 019, No. 2,726,162, No. 2,870,
No. 013, No. 2.983,611, No. 2,992,1
No. 09, No. 3.047,394, No. 3,057,72
No. 3, No. 3.103,437, No. 3,321,313
No. 3,325,287, No. 3,362,827, No. 3,539,644, No. 3,543,292,
British Patent No. 6.76.628, No. 825,544, No. 1.270,578, German Patent No. 872,153,
No. 1,090,427, Special Publication No. 34-7.133,
It is described in No. 46-1872.

Particularly preferred hardeners are aldehydes, active vinyl compounds and active halogen compounds.

The photographic emulsion layer of the photographic light-sensitive material used in the present invention is a dye-forming coupler, that is, color is formed by oxidative coupling with an aromatic primary amine developer (e.g., phenylene diamine derivative, amine phenol derivative, etc.) during color development processing. Contains compounds that can be used. For example, magenta couplers include pyrazoloazole couplers, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pipa There are cyan couplers such as naphthol couplers and phenol couplers.These couplers are non-diffusible and have a hydrophobic group called a noglast group in the molecule.
Or a polymerized one is preferable. The coupler is
It may be either 4-equivalent or 2-equivalent to silver ions.

Furthermore, in the present invention, in order to suppress staining and photobleaching over time, the following - drinking amount (I) or (n) 2 is used.
Particularly preferred is the case containing an equivalent magenta coupler.

General formula (I) (wherein, R1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za , Zb
and Zc each represent methine, substituted methine, =N- or 1 trillion, one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond.

The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, the case where R1 or X forms a dimer or more multimer is also included. Also, Za, Z
When b or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. ) General formula (n) (wherein, W represents a substituted aryl group, 2 represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and Y represents a substituted or unsubstituted acylamino group, ureido The group represents an anilino group.) Next, general formula (1) will be explained in detail.

- In terms of drinking cost CD, a multimer means one having two or more groups formed by "drinking cost CI" in one molecule, and bis forms and polymer couplers are also included therein. Here, the polymer kagra may be a homopolymer consisting only of a monomer (preferably one having a vinyl group, hereinafter referred to as a vinyl monomer) having a moiety which is formed by the alcoholic acid [I], or an aromatic polymer. Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of grade amine developers.

The compound represented by the general formula CI) is a 5-membered ring-5-membered ring fused nitrogen heterocyclic coupler. It has a structure. - Preferred compounds among the couplers represented by [■] are IH-imidazo ('1.2-b) pyrazoles, IH-pyrazolo (1
,s-b]pyrazoles, IH-pyrazolo[5,l-c
] [:l.

2.4,1) Liazoles, IH-pyrazolo[1°5-
b) C1,2,4)+-lyazoles, IH-pyrazolo(1,5-d)tetrazoles and IH-hy,y7”o
(1,5-a) benzimidazoles, each represented by -drinkage (:I [[) c■st (V) c■]c and [~■], and among these, particularly preferred The compound is represented by the general formula [■] and CM)〇(I[[) CIV)[■][
■〕 [■] [■] General formula [m] ~
In [~■], substituents R2, R3 and R4 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X is a hydrogen atom. Represents a group that can be separated by reaction (for example, a halodane atom, a carboxy group, or a group that bonds to a carbon at a coupling position via an oxygen atom, nitrogen atom, or sulfur atom and is capable of coupling off).

The case where R2, R3, R4 or X becomes a divalent group and forms a bis body is also included. Also, -drinking fee〔■〕～〔■〕
When the moiety represented by is in the vinyl monomer, R
2, R3 or R4 represents a simple bond or linking group, through which the vinyl group is bonded to the moiety represented by the general formulas [■] to ○1IID.

More specifically, R2, R3, and R4 are hydrogen atoms, halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, propyl group, -butyl group, trifluoromethyl group, tridecyl group, 3-(2,4-di-t-amylphenoxy)propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-heyacylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g., phenyl group, 4-t-butylphenyl group, 2 + 4-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-thienyl group, 2-
pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group,
-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-butylphenoxy group, etc.), heterocyclicoxy group (e.g., 2-benzimidazolyloxy group, etc.), acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), alpamoyloxy group (Example 1f, N-
7-enylcarbamoyloxy group, N-xf-carbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, Tetradecanamide group, α-(2,4-di-t-aminophenoxy)butyramide group, γ-(3-1-dityl-4-hyProxyphenoxy)butyramide group, α-(4-(4-hydroxyphenylsulfonyl) ) phenoxy) decanamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-10o-5-)F7' syloxycarzenylanilino group , N-acetylanilino group, 2-chloro-5-(α-(3-1-butyl-4-hyProxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group) , N
, N-dibutylureido group, etc.), imide group (e.g., N-dibutylureido group, etc.), imide group (e.g., N
-succinimide group, 3-penzylhydantoynyl group,
4-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), Alkylthio groups (e.g., methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-5'-t-octylphenylthio group, 3-e entadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), peterocyclic thio group (e.g. , 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, 2-benzothiazolylthio group, etc.),
y 4-tart-butylphenoxycaldenylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2 -Methyloxy-5-1
-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., t, N-ethylcarbasoyl, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N- dodecylcarbamoyl group, N-(3-(2,4-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-di-tert-amylphenoxy)acetyl group, benzoyl group) groups), sulfamoyl groups (e.g. ttf, N-ethylsulfamoyl groups,
N, N-cyclobylsul7amoyl group, N-(2-dodecyloxyether)sulfamoyl group, N-ethyl-N
-dodecylsulfamoyl group, N.

N-noethylsul7 amoyl group '4), sulfonyl group (
For example, methanesulfonyl group, octanesulfonyl group,
benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g., octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarynyl group (e.g., methoxycarbonyl group, butyloxycargonyl group, dodecylcarbonyl group,
octadecylcarbonyl group, etc.), aryloxycarbinyl group (N, t, phenyloxycarbinyl group, 3-
bentatecyloxy-carbonyl group, etc.>, and X represents a hydrogen atom, a halodane atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group linked with an oxygen atom (e.g., acetoxy group, Noyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4
-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-
Naphthoxy group, 7 3-nitadecylphenyl groups, benzyloxycar? nyloxy group, ethoxy group, 2-cyano, ethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-7-enyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.)
, a group linked via a nitrogen atom (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4,5゜6--27
Tafluoropenzamide group, octanesulfonamide group, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, 1-piveridyl group, 5,5-dimethyl-2,4-17oxo-3-oxazolidinyl group , 1-benzyl-ethoxy-3-hydantoynyl group, 2
N-1,1-dioxo-3(2H)-oxo-1,2-
Benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyrizonyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazole-1-
yl, 5-t fc halo-f o mohencitriazol-1-yl, 5-methyl-1゜2.3.4-
4 lyazol-1-yl group, benzimidazolyl group, 3
-benzyl-1-hydantoinyl group, 1-benzyl-5
-hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-piparoylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.) Groups connected by atoms (e.g., phenylthio group, 2-cal?
xyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2-(2-hexanesulfonylethyl )-5-tart-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-7enyl-2゜3.
4.5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2
-phenyl-3-dodecyl-1°2.4-)! J azolyl-5-thio group, etc.).

When R2, R3, R4 or X becomes a divalent group to form a bis body, this divalent group is described in more detail as follows:
Substituted or unsubstituted alkylene groups (e.g., methylene group, ethylene group, 1,10-decyleno group, -CI(2CH
2-0-CI (2CH2-1 etc.), substituted or unsubstituted ferene group (e.g. 1,4-phenylene group, 1,3-
phenylene group, -NHCO-R'-CONH- group (R' represents a substituted or unsubstituted alkylene group or phenylene group), etc.)
represents.

When the compound represented by the general formula (ill) to [■] is present in the vinyl monomer, the linking group represented by R2, R3 or R4 is an alkylene group (substituted or unsubstituted alkyref group, for example, methylene group, ethylene group, 1.10
-decyleno group, -CH2CH20CH2CH2-1, etc.)
, phenylene group (substituted or unsubstituted phenylene group,
For example, it is formed by combining those selected from 1,4-phenylene group, 1゜3-7 enylene group, -NHCO-1-CONH-1-〇-1-OCO-, and aralkylene group (e.g., t, etc.) In addition, the vinyl group in the vinyl monomer has the formula CIH)
It also includes cases in which it has substituents other than those represented by ~[■]. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g., methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide) , methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, uralyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β
-hydroxymethacrylate), methylene dibisacrylamide, vinyl esters, vinyl acetate, vinyl gropionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, novinyl benzene, vinylacetophenone and sulphostyrene), itafonic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-
Pyrrolidone, N-vinylpyridine, and 2- and 4
-Vinylpyri-sin etc. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of couplers represented by the general formulas [■] to [-■] above are described in the documents listed below.

The compound of general formula (III) is disclosed in JP-A-59-16254
No. 8, etc., the compound of formula C
No. 659, etc., the compound of formula [v] is
27411, etc., - Compounds of formula (V[] are described in JP-A-59-171956 and JP-A-60-172982, etc., - compounds of formula [■] are described in JP-A-60-33552, etc.
In addition, the compound of formula [■] is disclosed in U.S. Patent No. 3.
, No. 061, 432, etc., respectively.

Also, JP-A-58-42045, JP-A No. 59-21485
No. 4, No. 59-177553, No. 59-177544
The highly color-forming ballast group described in No. 1, No. 59-177557, etc. is applicable to any of the compounds of the above-mentioned formulas CI [[3 to [■]].

Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto.

-I M-2 Σ ΣΣ
Shiba ω ■Σ
Σ 2 Specification S (no change in content) Σ IJ 2C
J+ 1Σ
Σ Σ ΣΣ
Σ 1, I ′: 5 Σl
1Σ
Σ M-3・4 ・9 C8H17 (S M-37 M-41 C8H17(t) Σ Σ QNext, general formula (II) will be explained in detail. W is at least one halodane atom, alkyl represents a phenyl group or naphthyl group substituted with a group, an alkoxy group, an alkoxycarbonyl group, or a cyano group.

The alkyl group represented by 2 is a straight chain or branched alkyl group having 1 to 42 carbon atoms, an alkenyl group, a cycloalkyl group,
It represents an aralkyl group or an alkynyl group, and these include a halodane atom, hydroxy, mercapto group, cyano group, nitro group, carboxyl group, aryl group, alkoxy group,
Aryloxy group, heterocyclic oxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbinyloxy group, silyloxy group, carbamoyloxy group, phosphateoxy group, acylamino group, sulfonamide group, alkoxycarbonylamino group, aryloxy Aromatic heterocyclic groups such as carbonylamif group, diacylamino group, carbamoylamino group, sul-7 amoylamino group, pyrazolyl, imidazolyl, triazolyl, non-aromatic heterocyclic groups such as pyridino group, morpholino group, imido group, pyridone, monooxo nitrogen heterocyclic group such as saccharin, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group,
A silyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonyl group, an alkenyl group, an anilino group, etc. may be substituted.

The aryl group represented by 2 is a phenyl group or a naphthyl group having 6 to 46 carbon atoms, and these may be substituted with the substituents mentioned in the substituents for the alkyl group in addition to the alkyl group.

Furthermore, the heterocyclic group represented by 2 is a 5- to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, and a sulfur atom singly or simultaneously, and may be fused with a benzene ring. Representative petro ring skeletons include the following.

(In the formula, R5 represents a hydrogen atom, an alkyl group, or the same substituent as mentioned above for the substituent of the alkyl group, and R6 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an aryl The acylamino group represented by Y represents an alkanamide group having 1 to 42 carbon atoms or the benzamide group having 6 to 46 carbon atoms, and the ureido group represented by Y is an alkylureido group having 1 to 42 carbon atoms. , represents a 7-enylureido group having 6 to 46 carbon atoms, and the anilino group represented by Y has 6 to 46 carbon atoms.
represents a 722-amino group. These alkyl groups may have the same substituents as mentioned above for the alkyl group of X, and the phenyl group may have the same substituents as mentioned for the alkyl group of X above in addition to the alkyl group. It may have a group.

Among the 4-mercapto-5-monozolone type couplers represented by the general formula (II), particularly preferred couplers are represented by the following general formulas (IX) and (X).

- Formula (■) Ar General formula (x) A" In the formula, Ar represents a phenyl group substituted with at least one halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, or cyano group, and A represents Represents a halogen atom or an alkoxy group, R7 is a hydrogen atom,
Halogen atom, alkyl group, alkoxy group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, noacylamino group, alkoxycarbonyl group,
Alkoxysulfonyl group, aryoloxysulfonyl group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkyloxycarbonylamino group, ureido group, acyl group, nitro group, or carbonyl group represents a oxy group, R8 represents a halogen atom, a hydroxy group, an amino group, an alkyl group, an alkoxy group, an aryloxy group, or an aryl group, and R9 represents a hydrogen atom, an amino group, an acylamino group, a ureido group, an alkoxycarginylamino group. group, imido group, sulfonamido group, sul7amoylamino group, nitro group, alkoxycarbonyl group, carbamoyl group, acyl group, cyano group, alkylthio group, R4° is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, represents an alkoxy group or an aryl group, at least one of R8 and R4° represents an alkoxy group, m represents an integer of 1 to 3, and n represents an integer of 1 to 3.
represents an integer of 4, and t represents an integer of 1 to 3.

Also R1. represents an alkyl group or an aryl group,
R12 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an aryl group, and a
, b each represent an integer from 1 to 5.

More specifically, Ar is a substituted 7 enyl group, and examples of this substituent include halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom, etc.), alkyl groups having 1 to 22 carbon atoms (e.g. methyl group, ethyl group, tetradecyl group, t-budel group, etc.), alkoxy group having 1 to 22 carbon atoms (e.g., methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.), alkoxy group having 2 to 23 carbon atoms 1? Examples include a sifJkgnyl group (eg, tl', methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbinyl group, etc.) or a cyano group.

To explain A in more detail, 2 is a halogen atom (
For example, it represents a chlorine atom, a bromine atom, a fluorine atom, etc.), or an alkoxy group having 1 to 22 carbon atoms (for example, a methoxy group, an octyloxy group, a dodecyloxy group, etc.).

More specifically, R7 is a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group (e.g., a methyl group, a t-7'' thyl group,
2-methanesulfonamidoethyl group, t-butanesulfonylethyl group, tetradecyl group, etc.), alkoxy group (
For example, methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (such as acetamido group, benzamide group, butanamide group, tetradecaneamide group, α-(2,4-di-t
ert-amylphenoxy)acetamide group, α-(2
゜4-J-tart-amylphenoxy)butyramide group, α-(3--e entadecylphenoxy)hexanamide group, α-(4-hydroxy-3-tert-
butylphenoxy)tetradecanamide group, 2-oxo-pyrrolinon-1-yl group, 2-oxo-5-tetradecylpyrrolidin-1-yl group, N-methyl-tetradecanamide group, α-(3-methanesulfonamidophenoxy) ) tetradecaneamide group, etc.), sulfonamide group (
For example, methanesulfonamide group, benzenesulfonamide group, p-)luenesulfonamide group, octanesulfonamide group, p-dodecylbenzenesulfonamide group, N-methyl-tetradecanesulfonamide group, etc.)
Sulfamoyl group (e.g., N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N-(-3-
(dodecyloxy)-glopyl]sulfamoyl group, N
-[4-(2,4-tert-amylphenoxy)butyl]sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl group (e.g., N-methylcarbamoyl group, N-octadecylcarbamoyl group) group, N-(4-(2,4-di-tert-amylphenoxy)butyl]carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group (N-succinimide group, N-phthalimide group,
2,5-dioxo-1-oxasilinonyl group, 3-dodecyl-2,5-dioxo-1-hydantoynyl group, 3-
(N-acetyl-N-dodecylamino)succinimide group, etc.), alkoxycarbinyl group (e.g., methoxycarbinyl group, tetradecyloxycarbonyl group, pen/
Zyloxycarbonyl group), alkoxysulfonyl group (e.g., methoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group),
Aryloxysulfonyl group (e.g., phenoxysulfonyl group, 2.4-J-tert-amylphenoxysulfonyl group, !:”), alkanesulfonyl group (
flljt, methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexatecansulfonyl group, arylsulfonyl group (for example,
benzenesulfonyl group, 4-nonylbenzenesulfonyl group -' ), arylthio groups (e.g., phenylthio, p-t', ruthio, etc.), alkyloxycarbonylamino groups (e.g., ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxy-rumenylamino, etc.) , ureido group (e.g., N-methylureido group, N-7enylureido group, N,N-dimethylureido group, N-methyl-N
-dodecyllanide group, N-hexadecylureido group,
N.

N-diotadecylureido group, etc.), allele groups (e.g., acetyl group, benzoyl group, octadecanoyl group,
(p-dodecaneamide benzoyl group, etc.), a nitro group, or a carboxy group.

However, among the above substituents, those defined as alkyl groups have 1 to 42 carbon atoms, and those defined as aryl groups have 6 to 46 carbon atoms.

To describe R8 in more detail, R8 is a halogen atom (e.g., chlorine atom, bromine atom, etc.), hydroxy group, amine group (substituted or unsubstituted amino group, N-alkylamino group, N,N-dialkylamino group). group, N-anilino group,
N-alkyl-N-arylamino group, represents a peterocyclic amino group, e.g.) group, N, N-diacyl amino group, H
-bi-lysino group, N, N-bis(2-dodecyloxyethyl)amino group, N-cyclohexylamino group, N-
7enylamino group, N,N-bis(2-hexanesulfonylethyl)amino group, etc.), alkyl group (linear or branched alkyl group, aralkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, etc.), e.g. , methyl group, butyl group, octyl group, dodecyloxy group, benzyl group, cyclopentyl group, 2-methanesulfonylethyl group, 3-phenoxypropyl group, etc.L flukoxy group (
For example, methoxy group, butoxy group, benzyloxy group,
2-ethylhexyloxy group, dodecyloxy group, 2-
Methanesulfonylethyl group, 2-butanesulfonylethyl group, ingropyloxy group, 2-chloroethyl group, 3
-('2,4-di-tert-amylphenoxy)propyl group, 2-(N-methylcarbamoyl)ethoxy group,
Cyclopentyloxy group, 2-ethoxytetradecylolorobutyloxy group, 3-(N-butylcarbamoyl)propyloxy group, 3-(N,N-dimethylcarbamoyl)7Do pyloxy group, 4-methanesulfonylbutoxy group, 2- ethanesulfonamidoethyl group, etc.), aryloxy group (e.g., phenoxy, cy group, 2,
4-dichlorophenoxy group, etc.) or aryl group (substituted or unsubstituted phenyl group having 6 to 38 carbon atoms, α- or β
-represents a naphthyl group, such as a phenyl group, an α- or β-naphthyl group, a 4-10 lophenyl group, 4-t
-ff thylenyl group, methanesulfonamidophenyl group, 2,4-trimethylphenyl group, etc.), R5 is a hydrogen atom, an amine group (substituted or unsubstituted amine group, N-alkylamino group, N, N- alkylamino group, N-anilino group, N-alkyl-N-arylamino group, hete0
Represents a ring amino group, such as N-butylamino group, N,
N-diethylamino group, N-(2-(2,4-・sheet t
ert -amylphenoxy)ethyl]amine group, N
, N-butylamino group, N-pyritz group, N,
N-bis-(2-dodecyloxyethyl)amine group, N
-cyclohexylamino group, N, N-nohexylamino group, N-phenylamino group, 2,4-di, ert
-7 milphenylamino group, N-(2-10-5-tetradecanamidophenyl)amino group, N-methy#-
N-phenylamino group, N-(2-pyridyl)amino group, etc.), acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, (2,4-di-tert-amylphenoxy)acetamide group, 2-chloro benzamide group, 3-pentadecylbenzamide group, 2-(2-methanesulfonamidophenoxy) dodecanamide group, 2-(2-chlorophenoxy)tetradecanamide group, etc.), ureido group (Example 7, methylureido group, phenyl ureido group, 4-cyanophenylureido group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, totysyloxycarbinylamino group, 2-ethylhgyloxycarbynylamino group, etc.), imide group (e.g., N -succinimide group,
N-phthalimide group, N-hydantoinyl group, 5.5-
-/'Methyl-2.4-・dioxoxazole-3-
yl group, N-(3-octadecenyl)succinimide group, etc.), sulfonamide group (e.g., methanesulfonamide group, octane sulfonamide group, benzenesulfonamide group, 4-chlorobenzenesulfonamide group, 4-dodecylbenzenesulfonamide group) , N-methyl-N-benzenesulfonamide group, 4-dodecyloxybenzenesulfonamide group, hexadecanesulfonamide group, etc.)
, sulfamoylamino group (e.g., N-octylsulfamoylamino group, N,N-dipropylsulfamoylamino group, N-ethyl-N-phenylsulfamoylamino group, N-(4-butyloxy)sulfamoylamino group) famoylamino group, etc.), nitro group, alkoxycarbonyl group (e.g., methoxycarbonyl group, butquine carbonyl group, dodecyloxycarbonyl group, pennoloxycardenyl group, 1), carbamoyl group (e.g., N-octylcarbamoyl group, N, N-butylcarbamoyl group, N-
fynylcarpamoyl group, N-(:3-(2,4-not-amylphenoxy)prozyl]carbamoyl group, etc.), acyl group (e.g., acetyl group, benzoyl group, hexanoyl group, 2-ethyl group) hexanoyl group, 2-
chlorobenzoyl group, etc.), cyanogen group, alkylthio group (
For example, dodecylthio group, semi-sylthio group to 2-ethyl,
pennorthio group, 2-oxocyclohexylthio group, 2
-(ethyltetrazocacaate)thio group, 2-(dodecyloxyethyl)thio group, 3-phenoxypropylthio group, 2-dodecanesulfonylethylthio group, etc.), R4° is a hydrogen atom, and hydroxyl group R8 represents the same alkyl group, alkoxy group, or aryl group as mentioned above, and at least one of R6' and R10 represents an alkoxy group.

Further, R represents an alkyl group or an aryl group as described for R8, and R12 represents a hydrogen atom or a location atom, an alkyl group, an alkoxy group, or an aryl group as described for R8.

Next, specific examples of the magenta coupler represented by the general formula (II) used in the present invention are listed below, but the invention is not limited thereto.

(L C1゜α C cover α -g α m-12 m-170 α m-22 C2H5 α α α m-34 α It can be synthesized based on the methods described in Japanese Patent No. 55-62454, US Pat. No. 3,701,783, and the like.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide P coupler having a .zeta.last group. A specific example is U.S. Patent No. 2,
No. 407,210, No. 2,875,057, and No. 3,265.06. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
20, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4
, No. 401,752, No. 4,326,024, RD
18053 (April 1979), British Patent No. 1,425
, No. 020, West German Detei Publication No. 2,219,917, No. 2,261.361, No. 2,329,587, No. 2,433,812, etc. A typical example is the type yellow coupler. α-Pi-guroylacetanilide couplers have excellent color fastness, especially light fastness;
Benzoylacetanilide couplers provide high color density.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. 052,
No. 212, No. 4,146,396, No. 4,228
Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociation type described in , No. 233 and No. 4,296,200. Further, specific examples of phenolic couplers include U.S. Pat.
No. 01,17.1, No. 2.7-72.162, No. 2,895; 826, etc. Couplers capable of forming cyan dyes that are stable to humidity and temperature are preferably used in the present invention, typical examples of which include:
A phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002, U.S. Pat. No. 58,308, same No. 4.1
26゜396, same No. 4,334,011, same No. 4,
327°17°3, West German Patent Publication No. 3,329.7°
29 and European Patent No. 121,365, and the 2,5-cyacylamino-substituted phenolic couplers described in U.S. Pat. 2- described in the same No. 4,451.5'59 and the same No. 4.427,767- etc.
These include phenolic couplers having a phenylureido group at the 5-position and an acylamino group at the 5-position. Patent application No. 59-93605, No. 5-9-264277 and No. 5
The cyan coupler described in No. 9-268135, in which the 5-position of naphthol is substituted with a sulfonamide group, an amine P group, etc., also has excellent fastness of a colored image and can be preferably used in the present invention. It is also possible to use colored couplers that have a color correction effect, or couplers that release a development inhibitor or accelerator during development (so-called DIR couplers or DAR couplers).

As a colored coupler, U.S. Patent No. 4,163゜67
The yellow-colored magenta coupler described in No. 0 and Japanese Patent Publication No. 57-39413, or the best example in the United States, is also disclosed in European Patent No. 96,570 and West German Application No.
No. 3.234.5-33 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the above-mentioned special couplers may form dimers or higher polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat.
x, 820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Pat. No. 4,3
No. 67.282.

These couplers are generally added in an amount of 2 x 10 to 5' x 10 mol per mole of silver in the emulsion layer, preferably 5 x 10 -' mol per 1 x 10 -2 mol.
It will be done.

It is of course possible to use two or more types of the above couplers in the same layer in order to satisfy the characteristics required of a photosensitive material, or to add the same compound to two or more different layers. .

Couplers can be introduced into the silver halide emulsion layer using known methods, such as those described in U.S. Pat. Esters (e.g. acetyl citrate tri°
butyl), benzoic acid esters (e.g. octyl benzoate), alkylaminyl P (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. trimesic acid or organic solvents with a boiling point of about 30°C to 150°C, such as ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxy-ethyl acetate, methylseron. After dissolving in rub acetate etc., it is dispersed in hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention,
Any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

Silver chlorobromide emulsions having a silver bromide content of 10 mol % or more are preferably used in the present invention. To obtain an emulsion with sufficient sensitivity without increasing fog, the silver bromide content should be 2.
In some cases, it is preferable that the amount is 0 mol% or more. Reducing the silver bromide content not only improves the speed of development, but also reduces the equilibrium accumulation amount in the developing solution, which is determined by the relationship with the amount of replenisher, when a photosensitive material containing silver bromide is run in a processing solution. Bromine ions are present at a low concentration, and the rapid developability of the developer can be set high, which is preferable.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of up to about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used.

Two or more types of silver halide emulsions formed separately may be mixed and used.

A typical monodisperse emulsion is an emulsion in which silver halide grains have an average grain diameter of greater than about 0.1 micron, and at least about 95% by weight of the silver halide grains are within ±40% of the average grain diameter. The average grain diameter is about 0.25 to 2 microns, and at least about 95% by weight or quantity of the silver halide grains have an average grain diameter ± 2 microns.
Emulsions such as those within the range of 0% can be used in the present invention.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
ce and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,4
34゜226, 4,414,310, 4,43
It can be easily prepared by the methods described in No. 3,048, No. 4,439,520, and British Patent No. 2.112.157. When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Pat. No. 4,434,226, etc. is described in detail.

The crystal structure may be uniform, or it may be composed of different halogen compositions inside and outside (or may have a J-shaped structure).
No. 46, U.S. Patent No. 3,505°068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. Furthermore, silver halide (with different compositions) may be bonded by bi-taxial bonding.

Also, a mixture of particles of various crystal forms may be used (c).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No. 1
7643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the locations listed are shown in the table below.

Additive type RD17647 RD187161
Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 4 Brighteners
Page 24 7 Anti-stain agent Page 25 Right column Page 650 Left to right column 8 Dye image stabilizer Page 25 9 Hardener Page 26 Page 651 Left column 1
0) 2 Inder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 13 Static inhibitor Page 27 Same as above The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal film. The present invention also provides research and
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in Disclosure 17123 (July 1978).

Further, the photosensitive material of the present invention can be subjected to development processing in a generally customary manner, except that the water washing step is in accordance with the present invention.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-I N,N-diethyl-p-phinylene diamine D-22-ami7-5-quethylaminotoluene D-3
2-amino-5-(N-ethyl-N-laurylamino)
Toluene D-44-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminoaniline D-6N-ethyl- N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N,N-)methyl-p-phni Dilene diamine D-94-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, acid ferment salt, and p-)luenesulfonate. The amount of the aromatic-grade amine developing agent used is about 0.19 to about 20 g per 1 j of the developing solution, more preferably a concentration of about 0.59 to about 10 g.

Color developers useful in the present invention may contain various hydroxylamines as preservatives.

Although hydroxylamines can be used in the free amine form in color developers, it is better to use them in the water-soluble acid salt form in the film. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like. Hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of hydroxylamines may be an alkyl group (e.g.
carbon atoms (1 to 33) may be substituted. Preferred are hydroxylamines substituted with two alkyl groups (for example, having 1 to 3 carbon atoms).

The amount of hydroxylamine added is 11 parts D0 of color developer.
It is preferably 9 to 10 g, more preferably 0 to 5 I. If the stability of the color developer is to be maintained, and also from the viewpoint of fogging, it is preferable that the amount added be small.

Also, as preservatives, sodium sulfite, potassium sulfite,
It is preferable to contain an acetate salt such as sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carzenyl sulfite adduct. The amount of these added is preferably 0 to 21/l, more preferably O
I to 59/l, and if the stability of the color developer is maintained, the smaller the number, the better.

Other preservatives include JP-A Nos. 52-49828, 56-47038, 56-32140, and 59-
Aromatic polyhydroxy compounds described in US Pat. No. 160142 and US Pat. No. 3,746,544, hydroxyacetones described in US Pat. No. 3,615,503 and US Pat.
α-Aminocarzenyl compound described in No. 25, JP-A-57
Various metals described in JP-A-44148 and JP-A-57-53749, various saccharides as described in JP-A-52-102727, hydroxamic acids as described in JP-A-52-27638, JP-A-52-27638, etc.
α,α′-dicarbonyl compounds described in No. 9-160141, salicylic acids described in No. 59-180588, No. 5
Alkanolamines described in No. 4-3532, No. 56-
Poly(alkylene imine)s described in No. 94349, No. 5
Examples include gluconic acid derivatives described in No. 675647. Two or more of these preservatives may be used as required. In particular, a combination of an N,N-dialkyl-substituted hydroxylamine and an alkanolamine such as triethanolamine is preferred.The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 1.
1.0, the color developer may contain other known developer component compounds.

In order to maintain the above 1) H, it is preferable to use various buffering agents.

As buffering agents, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt/kT,
N dimethylglycine salt, leucine salt, norleucine salt,
Guanine salt, 3,4-dihuman-90xyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propane diol salt, valine salt, proline salt, trishydrodiaminomethane salt, lysine Salt etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of 9.0 or higher, and even when added to color developers, they have no effect on photographic performance. It is particularly preferable to use these buffering agents because they have the advantages of having no adverse effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate,
Potassium Carbonate, Sodium Bicarbonate, Potassium Bicarbonate, Trisodium Phosphate, Dipotassium Phosphate, Disodium Phosphate, Dipotassium Phosphate, Sodium Borate, Potassium Boronate, Sodium Tetraphor7ate (Borax), Potassium folate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5
Examples include sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). But why is it uninvented?
It is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mol/l or more, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/l.

In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

The chelating agent is preferably an organic acid compound, for example,
Tokuko Sho・↓No. 8-030496 and No. 44-30232
Aminopolycarmenic acids described in JP-A-5:6-97
347, Special Publication No. 56-39359 and West German Patent No. 22
Organic phosphonic acids described in No. 27639, JP-A-52-1
No. 02726, No. 53-42730, No. 54-121
No. 127, No. 55-126241 and No. 55-659
Examples include phosphonocarmenic acids described in Japanese Patent Publication No. 58-195845, Japanese Patent Publication No. 58-203440, and Japanese Patent Publication No. 53-40900. Preferred specific examples are shown below, but the invention is not limited thereto.

・Nitrilotriacetic acid e Noethylenetriaminepentaacetic acid-nitrilo-N,N,'N-trimethylenephosphonic acid ・Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid ・1,3-diamino-2- Pronominol-tetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-)aminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid-ethylenediamine orthohyde 1
．． II Oxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarzenic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-his(2-hydroxybenzyl)ethylenediamine-N,N'- Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, 1 is 0. It is about I11-10g.

Various development accelerators can be added to the color developer of the present invention. As a development accelerator, Japanese Patent Publication No. 37-1
Thioether compounds described in No. 6088, No. 37-5987, No. 38-7826, No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247; JP-A-52-49829 , and 50-155
p-7 unilene diamine compound described in No. 54: 4?
1977-137726, Special Publication No. 44-30074, 4? Kaisho 56-156826”liy and Kaisho 52-4
Quaternary ammonium salts described in U.S. Pat. No. 3429, etc.; p-aminophenols described in U.S. Pat. No. 2,610,122 and U.S. Pat.
No. 3, No. 3,128,182, No. 4,230,796
No. 3,253,919, Special Publication No. 41-11431
No. 2,482,546, U.S. Patent No. 2,596,9
Amine compounds described in Japanese Patent Publication No. 37-16088 and Japanese Patent Publication No. 42-2520, etc.
No. 1, U.S. Patent No. 3128183, Special Publication No. 41-114
No. 31, No. 42-23883 and U.S. Patent No. 3,532
, 501, etc., other 1-phenyl-3-pyrazolidones, hydrazines,
Menion type compounds, thione type compounds, imidazoles, etc. can be added as necessary. Particularly preferred are thioether compounds and 1-phenyl-3-pyrazolidones.

In the present invention, the color developer preferably contains bromine ions for the purpose of preventing fogging. As long as fogging does not occur, it is preferable that the content be small from the viewpoint of promoting development, and if the amount of replenishment is to be reduced, it is preferable that the content be large. In addition, as an inorganic antifoggant, a compound that provides chlorine ions, such as NO or m, may be added. Furthermore, various organic antifoggants can be added as necessary. Examples of organic antifoggants include adenines, benzimidazoles, benztriazoles, and tetrazoles.

It is preferable that the amount of these antifoggants added be as small as possible as long as fogging is prevented.
, OO1&~10,9 is preferred, and more preferably 0.
010g to 2g.

These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

The color developer of the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4,4'-diamino-
2,2'-disulfostilbene compounds are preferred. The amount added is preferably 0 to 5 ji/l, more preferably 0.
It is 1.9 to 2 fi/l.

Furthermore, various surfactants such as alkylphosphonic acid, arylphosphonic acid, aliphatic calzenic acid, and aromatic calzenic acid may be added as necessary.

The processing temperature of the color developer of the present invention is preferably 20 to 50°C, more preferably 30 to 40°C. The color development time is preferably 20 seconds to 3 minutes and 30 seconds, more preferably 3 minutes and 30 seconds.
It is 0 seconds to 2 minutes. Here, "color development time" refers to the time from when the photosensitive material comes into contact with the color developer until it comes into contact with the processing solution of the next bath, and also includes the so-called transfer time.

Is the replenishment amount 1rr of photosensitive material? It is preferably 20 to 600 TLl, more preferably 50 to 300++tA'.

Particularly preferably, it is 1 oom/~2007 nl.

In the present invention, a bleaching treatment is usually performed after color development. The bleaching treatment may be carried out simultaneously with the fixing treatment in a single bath bleach-fixing (Brix) process, or may be carried out separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents used in bleaching or bleach-fixing include organic complex salts of iron (e.g., amino-ricarzenic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarzenic acid, and organic phosphonic acids). (complex salts of) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; and hydrogen peroxide. Among these, organic complex salts of iron (I[[) are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (I[[)
Aminopolycarzenic acids, ami/polyphosphonic acids, or organic phosphonic acids or their salts useful for forming organic complexes include: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylene)7min-N-(β- oxyethyl)-N,
N', N'-triacetic acid, 1,2-diaminoprono-tetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexane diaminetetraacetic acid, 1,3-diamino- 2-propa/-/”FA acetic acid, methyliminodiacetic acid, iminoniacetic acid fermentation hydroxyl iminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminenipropionic acid, phenylenediaminetetraacetic acid 2-phosphonobutane-1,2,4-triacetic acid, 1,3-
・Quaminoprono-nol-N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,N,N ', N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron (II
I) Complex salts are preferred because they have high Genshiroba.

As the iron (n[) complex salt, one or more existing complex salts may be used, or iron (tIl) salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, A ferric ion complex salt may be obtained by reacting a chelating agent (such as aminopolycarzenic acid, aminopolyphosphonic acid, phosphonocarzenic acid, etc.) with a chelating agent (such as ferric phosphate) in a solution. When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be used in combination of two or more. In either case of forming a pre-formed complex salt or forming a complex salt, the chelating agent may be used in an amount greater than the stoichiometric amount. Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex may contain metal ions other than iron such as cobalt and copper, complex salts thereof, or hydrogen peroxide.

Persulfates for bleaching or bleach-fixing that can be used in the present invention include alkali metal persulfates such as potassium persulfate and sodium persulfate, or ammonium persulfate.

Bleach or bleach-fix solutions may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide). - Can contain a rogensing agent. Boric acid if necessary,
One or more inorganic and organic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Corrosion inhibitors such as ammonium nitrate and guanidine may be added to these alkali metal or ammonium salts.

The appropriate amount of bleach per ton of bleaching solution is 0.1 to 2 moles, and the preferred pH range of the bleaching solution is 0.5 to 8.0 in the case of ferric ion complex salts, especially aminobolicarzene. In the case of ferric ion complex salts of acid, amine biliphosphonic acid, phosphonocarzene, and organic phosphonic acid, it is 4.0 to 7.0. In the case of persulfates, p at a concentration of 0.1-2 mol/l
The range of H is preferably 1 to 5.

The fixing agents used for fixing or bleach-fixing are known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid; These are water-soluble silver halide solubilizers such as thioether compounds such as 6-cythio-1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Furthermore, in the bleach-fixing process, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.

For fixing or bleach-fixing processing, the fixer concentration is 0.2~
4 mol/l is desirable. In addition, in the bleach-fixing process,
The amount of ferric ion complex salt is 0.1 to 2 per ton of bleach-fix solution.
The mole of the fixing agent is preferably in the range of 0.2 to 4 moles. Further, the pH of the fixing and bleaching solution is usually preferably 4.0 to 9.0, particularly preferably 5.0 to 8.0.

The fixer or bleach-fixer may contain preservatives such as sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine, hydrazine, A bisulfite adduct of an aldehyde compound (for example, acetaldehyde sodium bisulfite) can be included. Furthermore, various fluorescent brighteners, antifoaming agents, surfactants, and common solvents such as polyvinylpyrrolidone and methanol can be contained.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their baths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A No. 53-32736, No. 53-57831, No. 374
No. 81, No. 53-65732, No. 53-72623, No. 53-95630, No. 53-95631, No. 5
No. 3-104232, No. 53-124424, No. 53
-141623, 53-28426, Research
Disclosure No. 517129 (July 1978)
Compounds having a mercapto group or disulfide group as described in JP-A-50-140129; thiazolidine derivatives as described in JP-A No. 45-8506;
Thiourea derivatives described in JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-58-16
Iodides described in West German Patent No. 966.410 and West German Patent No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others in Japanese Patent Publication No. 49-42434 , 49-59
No. 644, No. 53-94927, No. 54-35727
No. 55-26506 and No. 58-163940
Compounds described in the above-mentioned numbers and iodine and bromide ions can also be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a strong promoting effect, and are particularly preferred, as described in U.S. Patent No. 3,893,858 and West German Patent No. 1,290,81.
No. 2, JP-A No. 53-95630 is preferred.

After the fixing step or the bleach-fixing step, a washing step according to the invention is carried out as already described.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, each float, various squeegees, nitrogen agitation, air agitation, etc., as necessary.

(Example) Next, the present invention will be specifically explained according to an example. The following treatment steps were carried out continuously using the following treatment steps. Note that the processing time of the water washing process in this Prosensor is variable.

Time Temperature Tank capacity Color development process 3'30" 38℃±0.3℃ 6
01 Bleach-fixing process 1'30" 33℃±1℃ 4
01 water wash ■ 1'OO30℃±3℃ 201 water wash ■ 1'00 30℃±3℃ 201 water
Washing ■ 1'00 30°C±3°C zol Water washing process Three stages of countercurrent washing from washing (■) to water washing (2) were performed.

In addition, the amount of processing liquid brought in from various pre-tanks from the bleach-fixing process to washing with water is 40 ml/m3.

The replenishment amount in the color development process is 161 per m' of photosensitive material.
The solution used is as follows.

Color developer tank liquid replenisher water 800yu 8
00*J Nitrilotriacetic acid 3Na 2.0,
9 2.0g benzyl alcohol 14
m1 18m1 diethylene glycol
10ne 1out sodium sulfite
2.0g2.5.9Hydroxylamine sulfate
3.0g3.5p potassium bromide
1.0.9 - Sodium carbonate
30g 359N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-amine aniline sulfate 5.0p 8
．． Add 0.9 water to 10100O1
000+++lpH1o, 1s 10.65 Also, the replenishment amount in the bleach-fixing process is 60 per 1 m'' of photosensitive material.
It is m1. The solution used has the following formulation.

Bleach-fix tank liquid Replenisher water 4QQxl 400
m/ammonium thiosulfate (70% solution) 150d 300
:il sodium sulfite 18!9
36g Ethylenediaminetetraacetic acid iron (I [[) ammonium 55g 110g
Ethylenediaminetetraacetic acid/2Na 5. ! i! '
Add 10g water to 100
0 m/l OOOrt! PH6,706,50 Replenishment water in the washing step was carried out using Photosensitive Material 1 ni' p1oi.

Processing was performed on the photosensitive material with a width of 8.25cm using IE3180m.
Each test was carried out over a period of 90 days. Thereafter, various photosensitive materials were prepared as described below, and unexposed samples were processed using the processor water washing times shown in Table 1.

A multilayer silver halide color photosensitive material was prepared by coating the following first layer (lowest layer) to seventh layer (top layer) on a paper support laminated on both sides with polyethylene.

The coating solution for the first layer was prepared as follows. That is, yellow coupler 100I shown in Table 1 was dissolved in a mixture of 166.7 ml of dibutyl phthalate (DBP) and 200 at of ethyl acetate, and this solution was diluted to 1%
The emulsified dispersion was emulsified and dispersed in 800 g of a 10-thigelatin aqueous solution containing 80 g of a sodium dodecylbenzenesulfonate aqueous solution, and then this emulsified dispersion was made into a blue-sensitive silver chlorobromide emulsion (Br80%).
1450I (containing 66.7.p in Ag) was mixed to prepare a coating solution.

Coating solutions for the other layers were prepared in the same manner. The hardener for each layer is 2,4-dichloro-6-hydroxy-s-
Triazine sodium salt was used.

At this time, the amount of hardener added was adjusted for each photosensitive material so that the swelling degree shown in Table 1 was obtained.

The following spectral sensitizers were used for each emulsion.

Blue-sensitive emulsion layer; 3,3'-di(r-sulfopropyl)
- Selenacyanine sodium salt (2 x 10''4 moles per mole of silver halide) Green-sensitive emulsion layer: 3,3'-di(r-sulfopropyl)
-5,5'-diphenyl-9-ethyloxacalcecyanine sodium salt (2.5 x 10''-' mol per mol of silver halide) Red-sensitive emulsion layer; 3,3'-.di(r-sulfonate) Propyl)-9-methyl-thiadicyanine sodium salt (2.5 x 10 mol per mol of silver halide) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer; red-sensitive emulsion layer; The chemical structures of the compounds in the above table are as follows.

V-1 V-2 TJ V-3 C4H9(t) H CH3 郎α The structure of the magenta coupler used is as follows.

Magenta coupler (J) When using the above magenta coupler, the amount of silver in the green sensitive layer was set to 0.44 g/rr.

As is clear from the results in Table 1, if the swelling degree is smaller than the range of the present invention and the water washing time is shortened to 90 seconds or less (41-4, 22.27), Even when the yellow stain is high and the degree of swelling is larger than the present invention (melon 17-20, 26.31
．． ) Similarly, yellow stain concentration is high. Furthermore, when the treatment time is shorter than the water washing treatment time of the present invention, the yellow stain is high immediately after treatment and after aging even if the degree of swelling is within the range of the present invention (49, 17).

As mentioned above, the yellow stain that occurs immediately after processing and the increase in yellow stain that occurs over time in a process where the water washing process time is shortened to 30 to 90 seconds can be solved by using a photosensitive material whose degree of swelling is within the range of the present invention. I know it will happen.

Furthermore, in the present invention, when magenta couplers M-5 and m-11, which are described as preferred in the specification, are used (23-25, 28-30), the yellow color is lower than that when magenta force ply is used. It can be seen that there is less increase in stain over time, which is more preferable.

Example 2 Example 1 except for the water washing step as described below.
The same continuous process was performed. The amount of replenishment after washing is 1 m"'4 300 g of photosensitive material, and the washing time is approximately 300 g.
In (2), each test was carried out for 20 seconds for a total of 60 seconds. Washing temperature is 30℃±3℃. The recipe for the washing liquid is shown below.

Washing liquid water 950 Gobenzotriazole 1.5 g]-Hydroxyethylidene-1,1-i diphosphonic acid 2.09 Ammonium light bread lJ9 Ammonia water
Add Yuhiro water to pH 7.0
A sample prepared in the same manner as in Example 1 was processed using the processing solution obtained by processing the same photosensitive material as in Example 1 having a width of 1000 mm and a width of 8.25 α for 90 days at a rate of 180 m per day.

Yellow stain and 60 immediately after treatment as in Example 1
The yellow stain concentration was measured after aging for 8 weeks at a temperature of 70°C and a relative humidity of 70°C. The results are shown in Table 2.

Table 2 (R indicates a comparative example) **Washing time was 3 tanks with each tank having 20 seconds each (total 60 seconds).

As shown in Table 2, even in processing in which the amount of washing water replenishment is reduced to Daifuku (10), as in the case of normal washing, if a photosensitive material having a degree of swelling within the range of the present invention is used, the It was found that the yellow stain/concentration was low.

On the other hand, whether the degree of swelling is larger or smaller than the range of the present invention (1.5 to 4.0) (A32, 36, 37° 41.4
2.46) It can be seen that the yellow stain concentration is high.

Although the present invention is effective even when the amount of washing water replenishment is large,
This is particularly effective in water-saving processing where the amount of washing water replenishment is reduced.

Example 3 Table A is placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown below was created. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a) 19.1.9 and color image stabilizer (
b) 4. 27.2117 ethyl acetate and 7.9 g of solvent (c) were added to ΔI and dissolved, and this solution was mixed with 10 ml of sodium tidodecylbenzenesulfonate containing 8 III l of sodium tidedecylbenzenesulfonate.
The mixture was emulsified and dispersed in a 185% aqueous gelatin solution.

On the other hand, silver chlorobromide emulsion (silver bromide 80 matte, Ag 70
9/ktt (containing) and the blue-sensitive sensitizing dye shown below in an amount of 1 mol of silver chlorobromide f)7. A blue-sensitive emulsion containing OX 10-' moL was prepared in 90p. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table A to prepare a first layer coating solution. The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As various gelatin hardening agents, l-oxy-3,5-dichloro-3-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (silver halide 1 mot 5.OX 10-' m
ol addition) Green-sensitive emulsion layer (silver halide F per 1 mol) 4. OX 10-'
mol addition) (halogenated 9 l mot per F) 7
．． Addition of OX 10-5 mol) Red-sensitive emulsion layer (Silver halide 1 mol Todoro F) 1. OX 10-'
(Addition of mat) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer: 803, red-sensitive emulsion layer: 803, red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as cazoler, are as follows.

(&) Yellow coupler H3 (b) Color image stabilizer (c) Solvent (d) H H (,) Magenta coupler (f) Color image stabilizer H3CH5 (g) Solvent 2:1 mixture (weight ratio) of (h) Ultraviolet absorber 1:5:3 mixture (molar ratio) of (i) Color mixing prevention agent H H (j) Solvent (i3oC9H480+r-P=0 The emulsions used are shown in Table B below.

Table B After the obtained color photographic paper was imagewise exposed, it was processed using a Fuji Color Eper Processor PP-600 and the following processing steps. Each processing amount was carried out until three times the color developing tank was replenished for each condition.

The amount of 6 baths brought in was 35 m/m' of photosensitive material.

Processing process Time “Temperature color development 45 seconds 35℃ bleach fixing
45 seconds 35℃ rinse■ 20 seconds 35℃ rinse■
2o seconds 35℃ rinse ■ 20 seconds
Dry at 35℃ 50 seconds 80℃
(The rinsing liquid was flowed counter-currently in 3 tanks from rinsing ■→■→.

) The composition of each treatment liquid used is as follows.

Color developer tank liquid replenisher water
800 ml 800
m11-hydroxyethylidene-1,5go 1.
57I11.1-Diphosphonic acid (60% solution) Lithium chloride i, o, y
i, o9 diethylenetriaminepentaacetic acid 1,9
1.0.54.5-jihibuttonki-m-1,0,91
,5,9benzenedisulfonic acid sodium sulfite 0.5. ! ;'
1.0g potassium bromide 0. I
J-Sodium Chloride 15
．． 9-Adenine 30m
9 30m9 Potassium carbonate 40
．． @40pN-z Chill-N-(β-Meta 4
．． 5,9 8.0g sulfonamide P ethyl) -3-methyl-4-7minoaniline sulfate hyroxylamine sulfate 3.0. @ 4. □
y Fluorescent brightener (Sumitomo Chemical ■ 1.0g2.OgW
httex 4) Poly(ethyleneimine) 3.0. p
3.0.9 (50% aqueous solution) Add water 1000al 1000
ffi/KOHK-1: pH10
, 25 pH 10, 80 bleach-fix solution tank solution replenisher water 40
0 ml 400 ml ammonium thiosulfate
150mJ 300mA! (70%) Sodium sulfite 15,9 30
．． 9 Ethylene Quamine Tetraacetate Iron 55.9 1
10g (In) ammonium ethylenediaminetetraacetic acid sg 1og
2-Mercapto-5-ami7 1g 1g
-Add 3,4-thia diazole water 1000m/PH7,06
,5 Rinse solution (tank solution and refill solution have the same formulation) l-hydroxyethylidene-111-1,5m/diphosphonic acid (60
H) Nitrilotriacetic acid 1.0
p-nitrilo-N,N,N-trimethylene 1,0
9 ethylenediamine phosphonate Acetic acid 0.5
g! -11-V 7di7, near NNN'N'-tetrame 1. Q,! 9 ethylene phosphonic acid B 1 cts (40 tyrene aqueous solution)
0.50.9Mg5O4-7H2O0,20g ZnSOa
0.39 ammonium light/zeta
0.595-chloro-2-methyl-4-inch
30m9Azolin-3-one 2-methyl-4-inchazoline-310mCuone 2-octyl-4-inchazoline-10m93-one Ethylene glycol 1-5
! ! Sul-7 Anilamide 0
．． Ill, 2,3-benzotriazole 1
．． 0.9 Ammonium sulfite (40% aqueous solution)
1.09 Aqueous ammonia (26%) 2.611 III Rivinylpyrrolidone 1.0g
Fluorescent brightener (4,4'-diaminostyl 1.
Og harden type) Add water 100Qd
In KOH pH 7,
0 However, the replenishment amounts of the 6 liquids used are as follows.

Color developer 160 gin? Bleach-fix solution Loom//i In the same manner as for the color photographic paper shown in Tables A and B,
Color photographic papers with the magenta couplers and swelling degrees shown in the table were prepared, and after wedge-shaped exposure, the processing conditions (changes in rinsing time and amount of rinse replenishment) shown in Table 3 were applied using the Laninda solution. Processed.

The degree of swelling was obtained at various levels by changing the aging conditions after coating the resulting color photographic paper. The general conditions are as follows.

Swelling degree Aging condition 1.0 80℃ 20 hours -1,560℃
20 hours 2.5 40℃ 16 hours 3.5
30℃ 16 hours 4.5 25℃
80℃/70%R of each color photographic paper processed for 16 hours
Yellow stain concentration after 10 days at 80°C, magenta stain concentration after 4 weeks at 80°C, and xenon light (850°C)
Table 3 shows the results of measuring the fading rate of magenta density (DG=2.0) using a Macbeth densitometer after irradiation for 12 days (00 Lux, distance 50 tMt).

The magenta coupler used is as follows.

T> of the specification (no change in content) Magenta coupler Mouth μ (However, silver amount 0.321/m Magenta coupler) - CA' (Silver amount 0.32 JF/m Magenta coupler 12 Table 3) , when the degree of swelling is smaller than that of the present invention, yellow and magentastin are large (47R, 55R,
59R, 66R, 76R), and when the degree of swelling is greater than that of the present invention, yellow stain is particularly large and photobleaching is also undesirable.

Furthermore, scratches were often found on the front surface of the processed color photographic paper (51R, 62R, 73R).

Furthermore, if the amount of rinsing liquid refilled is significantly less than the amount of replenishment in the water-saving treatment that is normally performed, yellow and magenta stains will occur (52R).

63R, 70R) and other results, it can be seen from the results that the present invention can be used to effectively carry out water saving treatment for kanashi. Also, in the present invention, when the amount of rinse replenishment is significantly large, the photobleaching of magenta is somewhat inferior. Furthermore, if the washing time is shorter than in the present invention, yellow and magenta tint will occur (54R).

57R, 65R, 68R).

By processing the magenta coupler of the present invention under the processing conditions of the present invention, the most favorable photographic performance was obtained (6
0,61,67.69,71,72゜75. 77)
.

Example 4 Both sides subjected to corona discharge machining as described in Table CK.
1st layer (bottom layer) to 7th layer (
The top layer) was applied and a sample was prepared.

The coating liquid for the first layer was prepared as follows. That is, the yellow coupler 200 shown in Table C! i, anti-fading agent 93.3,9. High boiling point solvent (p) 10J and (q
) 51 and 600 d of ethyl acetate as an auxiliary solvent was heated and dissolved at 60°C, and then a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) 3300 containing 5% aqueous solution 330+11/
A coupler dispersion was prepared by emulsifying the mixture using Colo-Emil. Ethyl acetate was distilled off under reduced pressure from this dispersion, and emulsion x400.9 (Ag as 96.7I
, containing gelatin 170fi), and further added 10ti gelatin aqueous solution 2600.9 to prepare a coating solution.

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

n,2-(2-hydroxy-3,5-tert-
amyl phenyl) benzotriazole o 2-(2-hydroxy-3,5-d-tert-butylphenyl) benzotriazole p) (2-ethylhexyl) phthalate q dibutyl phthalate r 2.5-d-tert-amylphenyl-3,5 −
Di-tert-butyl hydroxybenzoate S2,
5-tert-octyl high P quinone t 1,4
-di-tert-amyl-2,5-dioctyloxybenzene u 2 g 2'-methylenebis(4-methyl-6-
(tert-butylphenol) The following were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide; green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3 '-Disulfoethyl oxacalzecyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy9.9'-(2,2-dimethyl,-1,3-pronog)) Thiadicarpicyanin iodine P Also, the following was used as a stabilizer for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-triazole and the following were used as anti-irradiation dyes.

4-(3-calcexy 5-hyproxy 4-(3-(
3-Calzexy-5-okine-1-(4-sulfonatophenyl)-2-pyrazolin-4-ylidene)-1-flobenyl)-1-pyrazolyl)benzenesulfonate-
Di-potassium salt N,N'-(4,8-dihyl'Oxy9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminemethanesulfonate)-tetrasodium salt 1,2-bis(vinylsulfonyl)ethane was used as a tagging agent.

Each coupler used has the following formula.

Yellow coupler α Magenta coupler Cyan coupler α The multilayer color photographic paper obtained as described above was subjected to the following processing steps after imagewise exposure until replenishing three times the amount of the color developing tank by modifying Fuji Film's FPRP115. , continuous processing was performed.

Color development 35℃ 45 seconds bleach fixing
35℃ 45 seconds rinse 1 35℃ 20 seconds rinse 2
35℃ 20 seconds rinse 3 35℃ 20 seconds rinse 4 35℃ 20 seconds dry 80℃ 60 seconds rinse 4
→ Countercurrent water washing to l.

The color developer used in the above processing step was as follows.

Color developer tank liquid replenisher water
800M1 800d diethylenetriaminepentaacetic acid 3.0p 3.0.
91-hydroxyethylide l, 5j*/ 1
．． 5jIj-1,1-diphosphonic acid (60%) Lithium sulfate 1.09 1.
0! i Potassium bromide 0.05,9
-Sodium sulfite 1.7i
L, 7i Sodium chloride 1.
5JF O,7Ii adenine
301R930II! 71.2.3-pensitriazo 2m9 5m9-potassium carbonate 41 40. !
1lN-ethyl-N-(β-meta 5.5,9
9.0! i sulfonamitoethyl) -3-methyl-4-amine aniline sulfate fluorescent brightener (Jinju Kagaku■ 1.1 2.5,9
Whi tax 4) Add water 1000g 1000i
7KOHK PH10,5011,0
The bleach-fix used in the processing step was the same as in Example 3. Regarding the rinsing liquid, the replenisher and tank liquid were the same, and the following ones were used.

Rinse liquid 5-chloro-2-methyl-4-inch 40rn
9 Azolin-3-one 2-methyl-4-isothiazolya 3 10m9
-one 2-octyl-4-inchazoline-10rn93-one bismuth chloride (40% aqueous solution) o, s
o! j Nitrilo-N,N,N-trimethylene
1.0 WLl phosphonic acid (40%) 1- and 1-10 xyethylidene-1,1-2,511j
・Diphosphonic acid (60%) Fluorescent brightener (4,4'-diaminostyl 1.
0g pen type) Ammonia water (26ch) 2
d Add water 1000j
At ljKOH -
The replenishment amounts of 7.0 color developer, bleach-fix solution, and rinse solution are 16011j, 60d, and 60d, respectively, for 1 color photographic paper.
It was 120 go.

Photosensitive materials were prepared in which only the magenta coupler was changed as shown in Tables c and o, and as in Example 3, the photosensitive materials whose degree of swelling was changed over time after coating were exposed in a wedge pattern, and the running liquid was Processed by using and changing only the rinse time (
(See Table 4 for details).

Regarding the obtained processed light-sensitive material, the stain density after aging and photobleaching over time were measured in the same manner as in Example 3 (with the exception that irradiation with a fluorescent lamp, 3000 Lux, and 4-month exposure at a distance of 30 lights) was carried out. The results are shown in Table 4. Table 4 (R is a comparative example) Table 4 shows that when the degree of swelling is smaller than that of the present invention, yellow and magenta tin are thicker (7sR, 7sR).

86R, 92R, 98R), the greater the degree of swelling, the greater the yellow stain, and the photobleaching of magenta also deteriorates (
84R, 85R, 88R, 94R.

100R). Furthermore, when the washing time is short, yellow and magenta tint are large. According to the configuration of the present invention, good photographic performance can be obtained, and further, if the preferred magenta coupler of the present invention is used, even better performance can be obtained (90
．． 91.93, 96°97.99).

Example 5 A multilayer color photographic paper having the layer configuration shown in the different faces of the magenta coupler was prepared on a paper support double-sided laminated with polyethylene. The coating solution was prepared as follows, containing yellow coupler (a) 19.19 and color image stabilizer (b).
) 4.49 to acetic acid fk 27.2 rrtt and solvent (c) 7. g- is added and dissolved, and this solution is diluted to 10%
1 containing 8 ml of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 yl of 0% gelatin aqueous solution.

On the other hand, silver bromide emulsion (silver bromide 1.0m0I1%, Ag7
A blue-sensitive emulsion 909 was prepared by adding the blue-sensitive sensitizing dye shown below to the blue-sensitive sensitizing dye shown below (containing 09/kg) in an amount of 5.0×10 moJ per mog of chlorobromide. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table B to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-8-to-I77 dine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

! Sensitive emulsion layer (silver halide 1 mol 5, OX 10 mo
b addition) Green-sensitive emulsion layer (silver halide 1 mo [4.0 x 10 mol)
Addition) (Silver halide 1 mol Schiff 0 x 10 m
oA' addition) is a sensitive emulsion layer I C2H5 units C2H5 (0.9 x 10 m per silver halide 1 rnoll)
ol addition) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler H3 (b) Color image stabilizer (c) Solvent (d) Color mixing inhibitor (e) Solvent (f) Color image stabilizer (g) Solvent (h) Ultraviolet absorber (1) Color mixing inhibitor
(, CH H 1 mixture (weight ratio)) Solvent (1soC9H,,0)-yP=○ Whisper Den Gojo!
However, by changing the amount of hardening agent, the degree of swelling was 1.0.2.0.4.0 as shown in Table 5.
．． 5.0 multilayer color photographic paper was prepared.

The color photographic paper obtained as described above was continuously processed in the same processing steps as in Example 4. However, the rinsing time is
The changes were made as shown in Table 5. Each processing amount was carried out until the tank capacity of the color developer reached three times. The processing solutions used are as follows.

Color developer tank liquid 3 mint triethanolamine 8910 gN, N
-diethylhydroxylamine 4,29 6
．． 09 Ethylenediaminetetraacetic acid 1.09
1.59 potassium carbonate 3
09309 Sodium chloride 1.4
09 0.109 Add water 10
100O! 10100O bleach-fix solution (tank solution and replenisher have the same formulation)) EDTA re(m) NH4,2H2
060gEDTA ・2NIL ・2H204 Ammonium tateosulfate (70%) 120mA' Sodium sulfite 16 9 Add water
1000:1LtpH5.5 Rinse solution (tank solution and refill solution have the same formulation) Add water
1000m/1) H7,0 The replenishment amount of each solution is color photosensitive material 1-this color developer
160 go bleach fixer
100mg rinse solution 20
It's 0go.

In the same manner as in Example 4, the stain density and magenta photobleaching over time after treatment in each running test were measured.

Table 5 (R narrows the comparative examples) According to the present invention, not only the increase in yellow stain and magenta stain after treatment is small, but also the photobleaching of magenta is small, while the total rinsing time is 30 If the degree of swelling is less than 2 seconds, the stain will increase significantly, and if the degree of swelling exceeds 4, the magenta photobleaching will be significantly degraded.

(Effects of the Invention) According to the present invention, a immersed color image with good staining immediately after processing and after aging can be obtained even when developing processing is performed with a shortened washing processing time of 30 to 90 seconds. Further, even if the washing process is a water-saving process, such a saturated color image can be obtained. Furthermore, by using a photosensitive material containing a specific magenta coupler, it is possible to obtain an excellent color image with good stain, especially after 8 o'clock.

Procedure chief 11l Shoda September 24, 1986

Claims (3)

[Claims] (1) In developing a silver halide color photographic light-sensitive material, a light-sensitive material whose photographic layer has a degree of swelling of 1.5 to 4.0 is processed in a water washing process for a total processing time of 30 to 90 seconds. An image forming method characterized by: (2) The amount of washing water refilled in the washing process is 0.5 to 5 of the amount brought in from the pre-bath per unit area of the color photographic light-sensitive material.
The image forming method according to claim (1), wherein the image forming method is 0 times. (3) Claims characterized in that the silver halide color photographic light-sensitive material contains at least one magenta coupler selected from the group of compounds represented by the following general formulas (I) and (II): The image forming method according to item (1) or item (2). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling reaction with an oxidized aromatic primary amine developer. Represents a group capable of leaving. Za, Zb, and Zc each represent methine, substituted methine, =
Represents N- or -NH-, and combines Za-Zb bond and Zb-
One of the Zc bonds is a double bond and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, 2 with R_1 or X
It also includes the case where a multimer of more than one mer is formed. Also, Za,
When Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. ) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, W represents a substituted aryl group, Z represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and Y represents a substituted or represents an unsubstituted acylamino group, ureido group or anilino group)