JP2534039B2 - Image forming method - Google Patents

Description

The present invention relates to an image forming method, and more specifically to an image forming method of a silver halide color photographic light-sensitive material which does not impair image storability even if the washing time is shortened. Regarding

(Prior Art) Many studies have been conducted so far on shortening the processing time of silver halide color photographic light-sensitive materials. For example, as a method of shortening the development time, a method of raising the temperature or pH of the developer or using a development accelerator is known. Further, as a method of shortening the desilvering process, a method of adding various accelerators is known.

To shorten the processing time, it is effective to shorten the washing process in addition to the shortening of the developing process and desilvering process. Conventionally, the water washing treatment time is generally 2 to 3 minutes.

By the way, when shortening the washing process, it is inevitable that the bleaching component and the fixing component are not sufficiently washed. In this case, it causes deterioration of image storability of the processed light-sensitive material,
Conventionally, various color fading inhibitors have been added to color light-sensitive materials for the purpose of improving image storability (for example, U.S. Pat. Nos. 2816028, 3457079, 3698909 and 3764337).
No., 3700455, etc.), water treatment process time is 1 minute 3
When the time is 0 seconds or less, these anti-fading agents are also ineffective. That is, if the iron complex present in the bleaching solution or the bleach-fixing solution is not sufficiently washed, the residual iron complex reacts with the residual coupler, causing a problem that the yellow stain increases during dark storage.

Further, in the case of long-term continuous processing, yellow and / or magenta color stains, which are considered to be mainly attributed to the oxide of the developing agent, adhere to the light-sensitive material, but the washing time is short as described in the present invention. In the case of time, cleaning of the above-mentioned deposit becomes insufficient, and a new problem arises as stains immediately after the treatment.

On the other hand, in the washing treatment process, a large-scale water-saving treatment method has been proposed in recent years with the main purpose of saving water resources and eliminating the need for washing pipes when installing a treatment machine. These techniques are described in JP-A-56-70549, JP-A-57-132146, and JP-A-5-132146.
7-8543, 58-18631, 59-184343. Ibid 59-18
Nos. 4345 and 58-14834 are disclosed.

When the above water-saving treatment is used and a short-time water washing as in the present invention is carried out, the washing effect in the water washing treatment step becomes more insufficient, and the problem of stain after the above-mentioned treatment and / or aging becomes more serious. Things turned out.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a processing method which does not impair the image storability and does not deteriorate the stain immediately after the processing even in the development processing in which the washing processing time is shortened, particularly in the long-term continuous processing. To provide.

Furthermore, the object of the present invention is to reduce the washing time, and even when a water-saving treatment is used, without impairing the image storability,
It is to provide a processing method that does not deteriorate the stain immediately after the processing.

(Means for Solving the Problems) In the development processing of silver halide color photographic light-sensitive material, the above-mentioned purpose is to reduce the total processing time of the photographic layer having the swelling degree of the photographic layer of 1.5 to 4.0 to 30 times. ~ 90 seconds, the replenishment rate of the washing process step is 120 ~ 300ml / m ^2, and it is effectively achieved by continuous processing in a countercurrent type of ² ~ 9 tanks. It has been found that the above objects can be achieved more effectively when the 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 water washing treatment in the present invention includes not only a usual “water washing treatment” but also a simple treatment method such as performing only a so-called “stabilization treatment” without providing a substantial water washing process. As described above, the “water-washing treatment” in the present invention is used in a broad sense as described above.

The washing treatment time in the present invention is 30 seconds to 1 minute 30 seconds, preferably 40 seconds to 1 minute 10 seconds. The term "washing time" as used herein refers to the time from the contact of the light-sensitive material with washing water to the arrival of the final step in the drying zone. When the washing step is a multi-stage countercurrent washing step of 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 "stabilization treatment" is carried out instead of the usual washing with water. If the washing time is less than 30 seconds, the yellow stain immediately after the treatment and after the passage of time is increased even if the swelling degree of the photographic layer is within the range of the present invention, which is not preferable.

Another object of the present invention is to carry out treatment with a shortened washing treatment 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 in practice. The amount of washing water in the usual "washing process" is difficult because it depends on the number of baths for multi-stage countercurrent washing and the amount of the pre-bath component of the light-sensitive material brought in, but it is difficult to define the washing water in the present invention. The pre-bath component of the process may be 1 × 10 ⁻⁴ or less. The "pre-bath" used in the present specification is generally a fixing solution or a bleach-fixing solution, but is not limited thereto. For example, in the case of 3-tank countercurrent washing, it is preferable to use about 1000 ml or more, and more preferably 5000 ml or more per 1 m ² of the light-sensitive material.

The water washing step is preferably a so-called water saving step, for example, a multi-stage countercurrent water washing with two or more tanks (for example, 2 to 9 tanks) to save the washing water. Further, it is more preferable to carry out a multistage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 instead of the usual water washing step. In this case, the pre-bath component for the final bath washing with water is preferably 5 × 10 ^-2 or less. In the case of these water-saving treatments or stabilization treatments, the replenishing amount of washing water or stabilizing solution is
0.5 to 50 of the amount of "pre-bath" carried in per unit area of photosensitive material
It is preferably doubled (depending on the capacity), more preferably 3 to 30 times.

Various compounds can be used for various purposes in the washing and stabilizing steps in the present invention. For example,
To prevent the development of various bacteria, mold and algae,
It is known to add bactericides and antifungal agents. For example, Journal of Antibacterial and
Antifungal Ages (J.Antibact.Antifun
g.Agents) vol.11, No.5, p207-223 (1983) and compounds described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal", or JP-A-57-8543. 57-58143, 57-97530, 58-105145, 58-13463
6, JP-A-59-91440, 126533, JP-A-59-184344, JP-A-59-185336, JP-A-60-239750, JP-A-60-239751,
JP-A-60-247241, JP-A-60-260952, JP-A-61-214
9, JP-A-61-28947, JP-A-61-28945, Japanese Patent Application No. 59-158
The compounds described in the specification of 475 and Japanese Patent Application No. 60-105487 and the use thereof can be applied. In particular, isothiazolone derivatives (2-octyl-4-isothiazolin-3-one, 5
-Chloro-2-methyl-4-isothiazolin-3-one), a sulfanilamide derivative (such as sulfanilamide), and a benzotriazole derivative (such as benzotriazole, 5-methyl-benzotriazole, 5-chloro-benzothiazole) It is useful. It is known to add various chelating agents for the purpose of improving the image stability after processing. For example, inorganic phosphoric acid, organic carboxylic acid, aminopolycarboxylic acid and organic phosphonic acid are useful, and they are disclosed in JP-A-57-8543, JP-A-57-197540, and JP-A-57-197540.
58-14834, JP-A-58-134636, JP-A-59-126533
No. 59-184343, No. 59-184344, No. 59-184344
59-184345, JP-A-59-185336, JP-A-60-135942
No. 60-238832, No. 60-239748, No. 60-239748
60-239749, JP-A-60-239750, JP-A-60-239751
No. 60-242458, 60-262161, and
61-4047, JP 61-4050, JP 61-4051, JP 61-4052, JP 61-4053, JP 61-4054.
The compounds and methods of use described in JP-A No. 61-28942, JP-A No. 61-28945, and the specification can be applied. In particular, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, ethylenediamine-NNN'N'-tetramethylphosphonic acid and nitrilo-NNN-trimethylenephosphonic acid are useful. Two or more of these chelating agents may be used in combination.

A metal compound can also be used in combination with these chelating agents. For example, a bismuth compound (JP-A-58-13
4636), Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Ti,
Compounds of Sn, Zn, Zr (JP-A-59-184344), Mg, Al,
Compounds of Sr (JP-A-59-185336) and the like, particularly Bi,
Compounds of Ca, Mg and Al are useful.

Furthermore, in order to effectively promote washing with water, a method of using a surfactant (Japanese Patent Laid-Open No. 57-197540) and a method of contacting with an ion exchange resin for the purpose of removing a component which exerts a bad influence (Japanese Patent Laid-Open No. Sho 60-1975) -220345), a method of reverse osmosis treatment (JP-A-60-241053), activated carbon, a viscous substance, a polyamide polymer compound, a polyurethane polymer compound, a phenol resin, an epoxy resin, a polymer compound having a hydrazide group. , A polymer compound containing polytetrafluoroethylene, a method of contacting with a monohydric or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer (JP-A-60-263151), electrodialysis treatment The method described in JP-A-61-28949 can be applied.

Further, a method of irradiating ultraviolet rays or passing a magnetic field can also be applied as a method of preventing the generation of pacteria and mold.

Furthermore, in the case of continuing the treatment, the method disclosed in JP-A-60-2336
No. 51, No. 60-235133, No. 60-263941, No. 61-4048
No. 61, No. 4040, No. 61-4055, No. 61-4056, No. 61
The methods of -4057, 61-4058, and 61-4060 can be applied.

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

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve the image storability.

As the various additives, the same or different target compounds may be used in combination of two or more depending on the purpose. From the viewpoint of the emulsion film substance (stickiness and the like) of the processed light-sensitive material, it is preferable that the addition amount be the minimum amount necessary for achieving the purpose.

In order to enhance the effect of washing out components in the film in washing or stabilizing treatment, it is preferable to circulate and agitate the liquid, and particularly, a method in which the liquid flow is strongly applied to the surface of the emulsion film of the light-sensitive material (for example, gas agitation, Spraying is good).

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen agitation, air agitation and the like may be provided in each treatment bath.

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

When the degree of swelling is less than 1.5, shortening the washing time as in the present invention (30 to 90 seconds) undesirably increases the yellow stain immediately after the treatment and after the passage of time. Also, when the degree of swelling is more than 4.0, the yellow stain density similarly becomes high, which is not preferable. Further, if the degree of swelling is more than 4.0, the mechanical strength of the photographic layer in the developing process is lowered to cause troubles such as scratches, and the amount of water absorption is increased, which causes a drying load, which is not preferable.

The photographic layer referred to herein means a laminated hydrophilic colloid group layer including at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like are included.

Any method may be used to adjust the degree of swelling within the scope of the present invention. It can be adjusted by changing the conditions or the aging conditions. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. You can

As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples are U.S. Pat.Nos. 2,614,928, 3,132,945, and 3,186,846.
No. 3,312,553; British Patent Nos. 861,414, 1,033,189
No. 1,005,784 and JP-B No. 42-26845.

As the gelatin-grafted polymer, a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene is grafted onto gelatin. Can be used. In particular,
A graft polymer of a polymer having some degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate is preferred. Examples of these are described in U.S. Pat. Nos. 2,763,625, 2,831,767, and 2,956,884. Representative synthetic hydrophilic polymeric substances are described, for example, in West German Patent Application (OLS) 2,312,708, U.S. Pat.
No. 751, No. 3,879,205, and Japanese Patent Publication No. 437561.

Examples of hardeners include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2 , 3-dihydroxydioxane), active vinyl compounds (1,3,5-
Triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6)
-Hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxic acid etc.), isoxazoles, dialdehyde starch, 2-chloro-
6-hydroxytriazinylated gelatin or the like can be used alone or in combination. Specific examples thereof are described in U.S. Patent Nos. 1,870,354, 2,080,019, 2,726,162,
2,870,013, 2,983,611, 2,992,109, 3,04
7,394, 3,057,723, 3,103,437, 3,321,313
No.3, No.3,325,287, No.3,362,827, No.3,539,644,
No. 3,543,292; British Patent Nos. 676,628; 825,544;
No. 1,270,578, German Patent 872,153, No. 1,090,427,
It is described in Japanese Examined Patent Publication Nos. 34-7,133 and 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, an aromatic primary amine developing agent (eg, phenylenediamine derivative or
Aminophenol derivatives, etc.) and compounds that can develop color by oxidative coupling. For example, as a magenta coupler, a pyrazoloazole coupler, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler,
There are cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), etc.,
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are non-diffusible ones having a hydrophobic group called a ballast group in the molecule,
Alternatively, a polymerized one is desirable. The coupler is
It may be either 4-equivalent or 2-equivalent with respect to silver ions.

Further, in the present invention, it is particularly preferable to contain a 2-equivalent magenta coupler represented by the following general formula (I) or (II) in order to suppress stain and photobleaching with time.

(Wherein, R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb, and Zc
Each represents methine, substituted methine, = N- or -NH-, one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond.

When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Further, the case where a multimer of dimer or more is formed by R ₁ or X is also included. When Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is also included. ) (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 unsubstituted acylamino group, ureido group or anilino group. Next, the general formula (I) will be described in detail.

In the general formula [I], a multimer means one having two or more groups represented by the general formula [I] in one molecule, and a bis form and a polymer coupler are also included in this.
Here, the polymer coupler may be a homopolymer composed of only a monomer having a moiety represented by the general formula [I] (preferably having a vinyl group, hereinafter referred to as a vinyl monomer), or an aromatic primary amine developer. Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of

The compound represented by the general formula [I] is a 5-membered-5-membered fused nitrogen heterocyclic coupler whose color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and is generally referred to as azapentalene. It has a structure. Preferred compounds among the couplers represented by the general formula [I] are 1H-imidazo [1,2-b] pyrazoles and 1H-pyrazolo [1,5-b]
Pyrazoles, 1H-pyrazolo [5,1-c] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5 -D] tetrazoles and 1H-pyrazolo [1,5-a] benzimidazoles, each of the general formula [III] [IV] [V] [VI] [VII]
And [VIII], and among them, particularly preferred compounds are those represented by the general formulas [V] and [VI].

In the general formulas [III] to [VIII], the substituents R ₂ , R ₃ and R ₄ 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, a hetero group. Ring oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamide group, carbamoylamino group,
Alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (for example, a halogen atom, a carboxy group, or a coupling position via an oxygen atom, a nitrogen atom or a sulfur atom). Represents a group capable of coupling off with a group bonded to carbon).

R ₂ , R ₃ , R ₄ or X may be a divalent group to form a bis-form. In addition, the general formula [III] ~ [VIII]
When the portion represented by is in the vinyl monomer,
R ₂ , R ₃ or R ₄ represents a simple bond or a linking group, and the moiety represented by the general formulas [III] to [VIII] is bonded to the vinyl group via this.

More specifically, R ₂ , R ₃ and R ₄ are hydrogen atom, halogen atom (eg chlorine atom, bromine atom etc.), alkyl group (eg methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl). Group, 3- (2,4-di-t
-Amylphenoxy) propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc., aryl group (for example, phenyl group, 4-t-butylphenyl) Group, 2,4-di-t-amylphenyl group, 4-
Tetradecanamidophenyl group etc.), heterocyclic group (eg 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group etc.), cyano group, alkoxy group (eg methoxy group, ethoxy group, 2- Methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-methylphenoxy group, 4-t-
Butylphenoxy group, etc.), heterocyclic oxy group (eg,
2-benzimidazolyloxy group etc.), acyloxy group (eg acetoxy group, hexadecanoyloxy group etc.), carbamoyloxy group (eg N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group etc.), silyloxy group ( For example, trimethylsilyloxy group etc.), sulfonyloxy group (eg dodecylsulfonyloxy group etc.), acylamino group (eg acetamide group, benzamide group, tetradecanamide group, α
-(2,4-di-t-aminophenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide Group), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2 -Chloro-5- {α
-(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group etc.), ureido group (for example, phenylureido group, methylureido group, N, N-dibutylureido group etc.), imide group (for example, N-succinimido group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimido group, etc.), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group, N- Methyl-N-decylsulfamoylamino group, etc.), alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3
-(4-t-butylphenoxy) propylthio group etc.),
Arylthio group (for example, phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4
-Tetradecanamide phenylthio group etc.), heterocyclic thio group (eg 2-benzothiazolylthio group etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, tetradecyloxycarbonylamino group etc.), aryloxycarbonyl Amino group (for example, phenoxycarbonylamino group, 2,4-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide) Group, octadecanesulfonamide group, 2-
Methyloxy-5-t-butylbenzenesulfonamide group, etc., carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl- N
-Dodecylcarbamoyl group, N- {3- (2,4-di-ter
t-amylphenoxy) propyl} carbamoyl group, etc.), acyl group (eg, acetyl group, (2,4-di-ter)
t-amylphenoxy) acetyl group, benzoyl group, etc.), sulfamoyl group (eg, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N-
(2-dodecyloxyethyl) sulfamoyl group, N-
Ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc.), sulfonyl group (for example, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), wolfinyl group (for example, Octansulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc., alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group) , 3-pentadecyloxy-carbonyl group, etc., and X is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group linked by an oxygen atom (eg, acetoxy group). Propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyl group,
Ethoxy oxaloyloxy group, pyrvinyloxy group,
Cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4
-Methanesulfonylphenoxy group, α-naphthoxy group,
3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group,
2-benzothiazolyloxy group, etc.), groups linked by nitrogen atoms (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4,5,6-penta group Fluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-3 (2H) -oxo-1,2
-Benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl,
5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl- 5-hexadecyloxy-
3-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.), and a sulfur atom. A group (for example, a phenylthio group, a 2-carboxyphenylthio group,
2-methoxy-5-t-octylphenylthio group, 4-
Methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert
-Octylphenylthio group, benzylthio group, 2-cyanoethyl group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2
-Benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,
4-triazolyl-5-thio group).

When R ₂ , R ₃ , R ₄ or X is a divalent group to form a bis derivative, the divalent group can be described in more detail. A substituted or unsubstituted alkylene group (eg, methylene group, ethylene group, 1,10-decylene _{group, -CH 2 CH 2 -O-CH} 2 CH
_2- , etc.), a substituted or unsubstituted ferrene group (for example,
1,4-phenylene group, 1,3-phenylene group, Etc.), —NHCO—R′—CONH— group (R ′ represents a substituted or unsubstituted alkylene group or phenylene group) and the like).

When the one represented by the general formulas [III] to [VIII] is in the vinyl monomer, the linking group represented by R ₂ , R ₃ or R ₄ is an alkylene group (a substituted or unsubstituted alkylene group , For example, methylene group, ethylene group, 1,10-decylene group, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.), phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group A 1,3-phenylene group, Etc.), —NHCO—, —CONH—, —O—, —OCO— and aralkylene groups (for example, Etc.) and groups that are established by combining those selected from the above.

The vinyl group in the vinyl monomer has the general formula [II
In addition to those represented by I] to [VIII], the case of having a substituent is also included. Preferred substituents are a hydrogen atom, a chlorine atom or a lower alkyl group having 1 to 4 carbon atoms.

Non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid,
α-chloroacrylic acid, α-alkacrylic acid (for example,
Methacrylic acid, etc.) and esters or amides derived from these acrylic acids (eg, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, taacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n -Butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, ularyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, Vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, vinyl Ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-2-
Pyrrolidone, N-vinylpyridine, and 2- and 4
-Vinyl pyridine and the like. It also includes the case where two or more non-color-forming ethylenically unsaturated monomers used here are used together.

Examples of compounds of the couplers represented by the general formulas [III] to [VIII], synthetic methods, and the like are described in the following documents.

The compound of the formula [III] is described in JP-A-59-162548,
The compound of the general formula [IV] is described in JP-A-60-43659 and the like, the compound of the general formula [V] is described in JP-B-47-27411 and the like, and the compound of the general formula [VI] is described in JP-A-60-43659. -171956 and 60-
In 172982 and the like, compounds of general formula [VII] are disclosed in JP-A-60-3
Nos. 3552 and the like, and compounds of the general formula [VIII] are described in U.S. Pat. No. 3,061,432 and the like.

Further, JP-A-58-42045, 59-214854, 59-1
Nos. 77553, 59-177544 and 59-177557, the highly chromogenic ballast group is represented by the above general formula [II
It applies to any of the compounds I] to [VIII].

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

Next, the general formula (II) will be described in detail.
Is at least one or more halogen atom, alkyl group,
It represents a phenyl group or a naphthyl group substituted with an alkoxy group, an alkoxycarbonyl group or a cyano group.

The alkyl group represented by Z is a linear or branched alkyl group having 1 to 42 carbon atoms, an alkenyl group, a cycloalkyl group,
Represents an aralkyl group or an alkynyl group, which are a halogen atom, hydroxy, a mercapto group, a cyano group, a nitro group, a carboxyl group, a freel group, an alkoxy group,
Aryloxy group, heterocyclic oxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, silyloxy group, carbamoyloxy group, phosphoric acid oxy group, acylamino group, sulfonamide group, alkoxycarbonylamino group, aryloxycarbonyl Amino group, diacylamino group, carbamoylamino group, sulfamoylamino group, pyrazolyl, imidazolyl, aromatic heterocyclic group such as triazolyl, piperidino group, morpholino group, non-aromatic heterocyclic group such as imide group, pyridone, Monooxo nitrogen heterocyclic group such as saccharin, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, silyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfoni Group, an alkenyl group, an anilino group, etc. may have been substituted.

The aryl group represented by Z is a phenyl group having 6 to 46 carbon atoms or a naphthyl group, which may be substituted with the alkyl group and the substituents described in the substituent of the alkyl group.

Further, the heterocyclic group represented by Z is a 5-membered to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, and a sulfur atom alone or simultaneously, and may be condensed with a benzene ring. The following are mentioned as a typical heterocyclic skeleton.

(In the formula, R ₅ represents a hydrogen atom, an alkyl group, or the same substituent as described in the substituent of the alkyl group, and R ₆ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or an alkylsulfonyl group. Represents an arylsulfonyl group.) The acylamino group represented by Y represents an alkaneamide group having 1 to 42 carbon atoms and a benzamide group having 6 to 46 carbon atoms, and the ureido group represented by Y is an alkyl group having 1 to 42 carbon atoms. The ureido group represents a phenylureido group having 6 to 46 carbon atoms, and the anilino group represented by Y represents a phenylamino group having 6 to 46 carbon atoms. These alkyl groups have the above-mentioned X
The alkyl group may have the same substituent as described above, and the phenyl group may have the same substituent as the alkyl group described in X above in addition to the alkyl group.

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

In the formula, Ar represents a phenyl group substituted with at least one halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cyano group, A represents a halogen atom or an alkoxy group, and R ₇ represents hydrogen. Atom, halogen atom, alkyl group, alkoxy group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, diacylamino group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group,
Represents an alkanesulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkyloxycarbonylamino group, ureido group, acyl group, nitro group, or carboxy group, and R ₈ represents a halogen atom, a hydroxy group, an amino group, an alkyl group Represents an alkoxy group, an aryloxy group or an aryl group, R ₉ is a hydrogen atom, an amino group, an acylamino group, a ureido group, an alkoxycarbonylamino group, an imide group, a sulfonamide group, a sulfamoylamino group, a nitro group, an alkoxy group. Carbonyl group,
Represents a carbamoyl group, an acyl group, a cyano group, an alkylthio group, R ₁₀ represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group, and at least one of R ₈ and R ₁₀ is an alkoxy group. Represents a group, m represents an integer of 1 to 3, n represents an integer of 1 to 4, and 1 represents an integer of 1 to 3.

R ₁₁ represents an alkyl group or an aryl group,
₁₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an aryl group, and a and b each represent an integer of 1 to 5.

More specifically, Ar is a substituted phenyl group, and as the substituent, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group). , A tetradecyl group,
t-butyl group), an alkoxy group having 1 to 22 carbon atoms (eg, methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.), an alkoxycarbonyl group having 2 to 23 carbon atoms (eg, methoxycarbonyl group, Ethoxycarbonyl group, tetradecyloxycarbonyl group, etc.) or cyano group.

More specifically, A is a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.) or an alkoxy group having 1 to 22 carbon atoms (eg, methoxy group, octyloxy group, dodecyloxy group, etc.). Represent.

If Re More particularly mentioned for R _7, R ₇ is a hydrogen atom, a halogen atom (e.g. a chlorine atom, a bromine atom, and fluorine atom), an alkyl group (e.g. methyl, t- butyl 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 (for example, acetamide group, Benzamide group, butanamide group, tetradecanamide group, α- (2,4-di-tert-
Amylphenoxy) acetamide group, α- (2,4-di-t
ert-amylphenoxy) butyramide group, α- (3-
Pentadecylphenoxy) hexanamide group, α- (4
-Hydroxy-3-tert-butylphenoxy) tetradecanamide group, 2-oxo-prolydin-1-yl group,
2-oxo-5-tetradecylpyrrolidin-1-yl group, N-methyl-tetradecanamide group, α- (3-methanesulfonamidephenoxy) tetradecaneamide group, etc.), sulfonamide group (for example, methanesulfonamide group, Benzenesulfonamide group, p-toluenesulfonamide group, octanesulfonamide group, p-dodecylbenzenesulfonamide group, N-methyl-tetradecanesulfonamide group, etc., sulfamoyl group (for example, N-methylsulfamoyl group, N -Hexadecylsulfamoyl group, N-[-3- (dodecyloxy) -propyl] sulfamoyl group, N- [4- (2,4-di-ter)
t-amylphenoxy) butyl] sulfamoyl group, N
-Methyl-N-tetradecylsulfamoyl group, etc.),
Carbamoyl group (for example, N-methylcarbamoyl group,
N-octadecylcarbamoyl group, N- [4- (2,4-
Di-tert-amylphenoxy) butyl] carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group (N-succinimide group, N-
Phthalimido group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1-hydantoinyl group, 3- (N-acetyl-N-dodecylamino) succinimide group, etc.), alkoxycarbonyl group ( For example, methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc., alkoxysulfonyl group (eg, methoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (eg, phenoxy group) Sulfonyl group, 2,4-di-tert-amylphenoxysulfonyl group, etc.), alkanesulfonyl group (for example, methanesulfonyl group, octanesulfonyl group, 2-
Ethylhexanesulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (for example, benzenesulfonyl group, 4-nonylbenzenesulfonyl group, etc.),
Alkylthio group (for example, ethylthio group, hexylthio group, benzylthio group, tetradecylthio group, 2- (2,4
-Di-tert-amylphenoxy) ethylthio group etc.),
Arylthio group (eg, phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino group (eg, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), ureido group (eg, N -Methylureido group, N-phenylureido group, N, N-dimethylureido group, N-methyl-N-dodecylureido group, N-hexadecylureido group, N, N-dioctadecylureido group, etc., acyl group ( For example, it represents an acetyl group, a benzoyl group, an octadecanoyl group, a p-dodecanamidobenzoyl 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.

Stated in more detail R _8, R ₈ is a halogen atom (e.g., chlorine atom, bromine atom, etc.), hydroxy group, an amino group (a substituted or unsubstituted amino group, N- alkylamino, N, N- dialkyl Amino group, N-anilino group, N-
It represents an alkyl-N-arylamino group or a heterocyclic amino group, and includes, for example, an N-butylamino group, N, N-dibutylamino group, N, N-dihexylamino group, N-piperidino group, N, N-bis ( 2-dodecyloxyethyl) amino group, N-cyclohexylamino group, N-phenylamino group, N, N-bis (2-hexanesulfonylethyl) amino group, etc.), alkyl group (linear or branched alkyl group, Represents an aralkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, for example, a methyl group, a butyl group,
Octyl group, dodecyloxy group, benzyl group, cyclopentyl group, 2-methanesulfonylethyl group, 3-phenoxypropyl group, etc.), alkoxy group (for example, methoxy group, butoxy group, benzyloxy group, 2-ethylhexyloxy group, dodecyl Oxy group, 2-methanesulfonylethyl group, 2-butanesulfonylethyl group, isopropyloxy group, 2-chloroethyl group, 3- (2,4-di-ter
t-amylphenoxy) propyl group, 2- (N-methylcarbamoyl) ethoxy group, cyclopentyloxy group,
2-ethoxytetradecyloxy group, 4,4,4,3,3,2,2-
Heptafluorobutyloxy group, 3- (N-butylcarbamoyl) propyloxy group, 3- (N, N-dimethylcarbamoyl) propyloxy group, 4-methanesulfonylbutoxy group, 2-ethanesulfonamidoethyl group, etc.),
Aryloxy group (for example, phenoxy group, 2,4-dichlorophenoxy group, etc.) or aryl group (having 6 to 38 carbon atoms)
Represents a substituted or unsubstituted phenyl group, α- or β-naphthyl group, for example, a phenyl group, an α- or β-naphthyl group, a 4-chlorophenyl group, a 4-t-butylphenyl group, a methanesulfonamidophenyl group. , 2,4-dimethylphenyl group, etc., R ₅ is a hydrogen atom, amino group (substituted or unsubstituted amino group, N-alkylamino group, N, N-dialkylamino group, N-anilino group, N-alkyl) -N
Represents an arylamino group or a heterocyclic amino group, for example, N-butylamino group, N, N-diethylamino group, N-
[2- (2,4-di-tert-amylphenoxy) ethyl]
Amino group, N, N-dibutylamino group, N-piperidino group, N, N-bis- (2-dodecyloxyethyl) amino group, N-cyclohexylamino group, N, N-di-hexylamino group, N- Phenylamino group, 2,4-di-tert-amylphenylamino group, N- (2-chloro-5-tetradecanamidophenyl) amino group, N-methyl-N-phenylamino group, N- (2-pyridyl) Amino group, etc.),
Acylamino group (for example, acetamide group, benzamide group, tetradecanamide group, (2,4-di-tert-amylphenoxy) acetamide group, 2-chlorobenzamide group, 3-pentadecylbenzamide group, 2- (2-methanesulfone group) Amidophenoxy) dodecane amide group, 2
-(2-chlorophenoxy) tetradecanamide group etc.), ureido group (eg methylureido group, phenylureido group, 4-cyanophenylureido group etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, dodecyloxycarbonyl group) Amino group, 2
-Ethylhexyloxycarbonylamino group, etc., imide group (for example, N-succinimide group, N-phthalimido group, N-hydantoinyl group, 5,5-dimethyl-2,4-dioxooxazol-3-yl group, N- (3-octadecenyl) succinimide group and the like), sulfonamide group (for example, methanesulfonamide group, octanesulfonamide group, benzenesulfonamide group, 4-chlorobenzenesulfonamide group, 4-dodecylbenzenesulfonamide group, N-methyl- N-benzenesulfonamide group, 4
-Dodecyloxybenzenesulfonamide group, hexadecanesulfonamide group, etc.), sulfamoylamino group (for example, N-octylsulfamoylamino group, N, N
-Dipropylsulfamoylamino group, N-ethyl-N
-Phenylsulfamoylamino group, N- (4-butyloxy) sulfamoylamino group, etc.), nitro group, alkoxycarbonyl group (for example, methoxycarbonyl group,
Butoxycarbonyl group, dodecyloxycarbonyl group,
Benzyloxycarbonyl group etc.), carbamoyl group (for example, N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-phenylcarbamoyl group, N- [3
-(2,4-di-tert-amylphenoxy) propyl] carbamoyl group etc.), acyl group (for example, acetyl group, benzoyl group, hexanoyl group, 2-ethylhexanoyl group, 2-chlorobenzoyl group etc.), cyano Group, alkylthio group (for example, dodecylthio group, 2-ethylhexylthio group, benzylthio group, 2-oxocyclohexylthio group, 2- (ethyltetradecanoate) thio group, 2-
(Dodecylhexanoate) thio group, 3-phenoxypropylthio group, 2-dodecanesulfonylethylthio group, etc., and R ₁₀ is a hydrogen atom, a hydroxyl group or R
The same alkyl group, alkoxy group and aryl group as those mentioned in _{8 above} are represented, and at least one of R ₆ and R ₁₀ represents an alkoxy group.

R ₁₁ represents the same alkyl group or aryl group as described for R ₈ , and R ₁₂ represents a hydrogen atom or the same halogen atom, alkyl group, alkoxy group or aryl group as described for R ₈ .

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

The magenta coupler used in the present invention is, for example, JP-B-53-34044, JP-A-55-62454, or U.S. Pat.
It can be synthesized based on the method described in the specification of 3,701,783.

Representative examples of the yellow coupler that can be used in the present invention include a hydrophobic acylacetamide-based coupler having a ballast group. A specific example is U.S. Pat.
No. 7,210, No. 2,875,057 and No. 3,265,06. In the present invention, the use of a 2-equivalent yellow coupler is preferable, and U.S. Pat. Nos. 3,408,194 and 3,44 are used.
No. 7,928, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-A-58-10739, U.S. Pat.
326,024, RD18053 (April 1979), British Patent 1,425,
No. 020, West German Application Publication No. 2,219,917, No. 2,261,361
No. 2,329,587, No. 2,433,812 and the like, nitrogen atom-releasing yellow couplers described in JP-A No. 2,329,587 and No. 2,433,812 are typical examples. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenolic couplers are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Couplers capable of forming a cyan dye that is fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include an ethyl group or more at the meta 1-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Phenol cyan coupler having an alkyl group, U.S. Pat.
No. 2,162, No. 3,758,308, No. 4,126,396, No. 4,3
34,011, 4,327,173, West German Patent Publication 3,329,729
2,5-diacylamino-substituted phenol couplers described in U.S. Pat.No. Examples include phenol couplers having a phenylureido group at the 5-position and an acylamino group at the 5-position. Japanese Patent Application Sho 59-9360
5, the cyan couplers described in 59-264277 and 59-268135 in which the 5-position of naphthol is substituted with a sulfonamide group or an amide group are also excellent in the fastness of a color image and are preferably used in the present invention. it can. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor or a development accelerator with development (so-called DIR coupler or DAR coupler) may be used.

Examples of colored couplers include yellow-colored magenta couplers described in U.S. Pat.
Typical examples include magenta colored cyan couplers described in 8,258 and British Patent 1,146,368. Other colored couplers are described in Research Disclosure 17643, Sections VII-G.

The DIR coupler that releases the development inhibitor is the above-mentioned RD17643,
The couplers of the patents described in Sections VII-F are useful.

In addition to the DIR coupler, the product of the coupling reaction may be colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.

In addition to the DIR coupler, a compound that releases a photographically useful residue during development may be contained in the light-sensitive material.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

These couplers are generally used in an amount of 2 × 10 ^-3 mol to 5 × 10 ^-1 mol, preferably ¹ × 10 ^-1 mol, per mol of silver in the emulsion layer.
^-2 mol to 5 × 10 ^-1 mol is added.

The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (eg, dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (eg diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citrate esters (eg acetyl citrate tributyl), benzoate esters (eg octyl benzoate) ), Alkyl amides (eg diethyl lauryl amide), fatty acid esters) such as dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate), etc., or organic solvents having a boiling point of about 30 ° C. to 150 ° C. Hydrophilic colloid after being dissolved in, for example, lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetoate, methyl cellosolve acetate, etc. Dispersed in. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

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.

The silver chlorobromide emulsion having a silver bromide content of 10 mol% or more is preferably used in the present invention. The silver bromide content is preferably 20 mol% or more in order to obtain an emulsion having sufficient sensitivity without increasing fog, but 20 mol% or less or 10 mol% or less is required particularly when rapidity is required. It may be preferable to use Reducing the silver bromide content not only improves the speed of development, but also when the photosensitive material containing it is run in the processing solution, the equilibrium accumulated amount determined by the relationship with the amount of replenisher in the developing solution. Since the bromine ion of 1 is present in a low concentration, the rapid developing property of the developer itself can be set high, which is preferable.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be a so-called Regular particle having a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere, a crystal defect such as a twin, or a composite form thereof. Good.

The grain size of the silver halide may be fine grains of about 0.1 μm or less, or large grains having a projected area diameter of about 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

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

A monodisperse emulsion is silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about
Emulsions such that 95% by weight are within ± 40% of the average grain diameter are typical. Average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% by volume
The emulsion in which the silver halide grains of the formula (1) are within the range of an average grain diameter of ± 20% can be used in the present invention.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like. When tabular grains are used, there are advantages such as improvement in color sensitization efficiency by a sensitizing dye, improvement in graininess and increase in sharpness, which are described in detail in U.S. Patent No. 4,434,226 cited above. ing.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146, U.S. Patent Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58-
No. 248469 is disclosed. Further, silver halides having different compositions may be joined by an epitaxial junction.

 Also, a mixture of particles having various crystal forms may be used.

The emulsion of the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is Research Disclosure No. 17643
And No. 18716, and the relevant locations are summarized in the table below.

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

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
The present invention can also be applied to black-and-white light-sensitive materials utilizing a mixture of three-color couplers described in the above.

The light-sensitive material of the present invention can be subjected to development processing by a generally-used method except that the washing step is according to the present invention.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and typical examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 N-ethyl-N- (Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylene Diamine D-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline These p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per developing solution.

The color developing solution used in the present invention may contain various hydroxyamines as a preservative.

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

Addition amount of hydroxylamine per color developer
The amount is preferably 0 to 10 g, more preferably 0 to 5 g. If the stability of the color developing solution is maintained, and also in terms of fog, it is preferable that the addition amount be small.

Further, as preservatives, it is preferable to contain sulfite salts such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts. The addition amount of these is preferably 0g ~ 20g /, more preferably 0g
It is ~ 5 g /, and a smaller amount is preferable if the stability of the color developing solution is maintained.

Other preservatives include JP-A Nos. 52-49828 and 56-4.
Nos. 7038, 56-32140, 59-160142 and U.S. Pat.
Aromatic polyhydroxy compounds described in 746544, US Patent 36
15503 and hydroxyacetones described in U.S. Pat.No. 1,306,176, α described in JP-A Nos. 52-143020 and 53-89425.
-Aminocarbonyl compounds, JP-A-57-44148 and JP-A-5-44148
Various metals described in 7-53749, various saccharides described in JP-A-52-102727, hydroxamic acids described in 52-27638, α, α'-dicarbonyl compounds described in 59-160141, Examples thereof include salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, poly (alkyleneimine) s described in No. 56-94349, and gluconic acid derivatives described in No. 56-75647. it can. If necessary, two or more kinds of these preservatives may be retained. In particular, N, N-
A combination of a 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
-12, more preferably 9-11.0, and the color developing solution may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy salt Phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-
Propanediol salt, valine salt, proline salt, trishydrosiaominomethane salt, lysine salt and the like can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent solubility and buffering ability in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they are effective for photographic performance. It is particularly preferable to use these buffers because they have no ill effects (fogging, etc.) and have an advantage that they are inexpensive.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium acid, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol /
The above is preferable, and 0.1 mol / to 0.4 mol / is particularly preferable.

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

The chelating agent is preferably an organic acid compound, for example, aminopolycarboxylic acids described in JP-B-48-030496 and 44-30232, JP-A-56-97347, and JP-B-56-3.
Organic phosphonic acids described in 9359 and West German Patent 2227639, JP-A Nos. 52-102726, 53-42730, and 54-12112.
No. 7, No. 55-126241 and No. 55-65956, and other phosphonocarboxylic acids described in JP-A Nos. 58-195845 and 58-
Examples thereof include compounds described in 203440 and Japanese Patent Publication No. 53-40900. Preferred specific examples are shown below, but the invention is not limited thereto.

・ Nitrilotriacetic acid ・ Diethylenetriaminepentaacetic acid ・ Nitrilo-N, N, N-trimethylenephosphonic acid ・ Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid ・ 1,3-Diamino-2-propanol-4 Acetic acid, transcyclohexanediaminetetraacetic acid, nitrilotriapropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminotetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediaminoorthohydroxyphenylacetic acid, 2-phosphonobutane -1,2,4-Tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid These chelating agents are necessary Two or more types may be used in combination depending on the case.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g per unit.

Various development accelerators can be added to the color developing solution of the present invention. As a development accelerator, Japanese Patent Publication No. 37-16
No. 088, No. 37-5987, No. 38-7826, No. 44-12380,
Thioether compounds described in U.S. Pat. No. 45-9019 and U.S. Pat. No. 3,813,247; JP-A Nos. 52-49829 and 50-155;
A p-phenylenediamine compound described in JP-A-54;
50-137726, JP-B-44-30074, JP-A-56-156826
And the quaternary ammonium salts described in JP-A-52-43429; p- in US Pat. Nos. 2,610,122 and 4,119,462.
Aminophenols; US Pat. Nos. 2,494,903 and 3,128,1
No. 82, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-1143
1, U.S. Patents 2,482,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc .; JP-B-37-16088
No. 42-25201, U.S. Patent No. 3128183, Japanese Patent Publication No. 41-11.
No. 431, 42-23883 and polyalkylene oxides described in U.S. Pat.
If necessary, 3-pyrazolidones, hydrazines, mesoionic compounds, thione compounds, imidazoles, etc. can be added. Particularly, thioether compounds and 1-phenyl-3-pyrazolidones are preferable.

In the present invention, the color developer preferably contains bromine ions for the purpose of preventing fog. From the viewpoint of promoting development, the content is preferably low as long as fog does not occur, and when the replenishment amount is reduced, the content is preferably high. In addition, as the inorganic antifoggant, a compound that gives a chlorine ion such as NaCl or KCl may be added. Further, various organic antifoggants can be added if necessary. Examples of the organic antifoggants include adenines, benzimidazoles, benztriazoles, and tetrazoles.

The addition amount of these antifoggants is preferably as small as possible so long as fog is prevented,
The amount is preferably 0.001 g to 10 g, more preferably 0.010 g to 2 g.

These antifoggants may be eluted from the color light-sensitive material during processing and accumulated in the color developing solution.

The color developer of the present invention preferably contains a fluorescent whitening agent. Fluorescent brighteners include 4,4'-diamino-
2,2'-disulfostilbene compounds are preferred. The addition amount is preferably 0 to 5 g /, more preferably 0.1 g to 2 g /
Is.

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

The processing temperature of the color developing solution of the present invention is preferably 20 to 50 ° C, more preferably 30 to 40 ° C. Color development time is 20
Second to 3 minutes and 30 seconds are preferable, and 30 seconds and 2 minutes are more preferable. The term "color development time" as used herein refers to the time from the contact of the light-sensitive material with the color developing solution to the contact with the processing solution of the next bath, and also includes so-called moving time.

The replenishing amount is preferably ^{20 to} 600 ml, and more preferably 50 to 300 ml per 1 m ² of the light-sensitive material. Particularly preferably 100 ml to 20
It is 0 ml.

In the present invention, bleaching is usually carried out after color development. The bleaching treatment may be performed in a single-bath bleach-fixing (blix) at the same time as the fixing treatment, or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. As a bleaching agent used in the bleaching treatment or the bleach-fixing treatment, for example, iron (III) is used as an organic complex salt (for example, aminodicarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid). Complex salts) or organic acids such as citric acid, tartaric acid, malic acid; persulfates; hydrogen peroxide. Among these, organic complex salts of iron (III) are preferable from the viewpoint of rapid processing and prevention of environmental pollution. The aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β -Oxyethyl) -N,
N ', N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2- Propanol tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine dipropionacetic acid, phenylenediamine tetraacetic acid, 2-phosphonobutane -1,2,4-triacetic acid, 1,3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1 , 3-Propylenediamine-N, N, N ', N'-tetramethylenephos Phosphate, 1-hydroxyethylidene-1,1'-diphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power.

The iron (III) complex salt may use one or more ready-made complex salts, or an iron (III) salt (eg, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, phosphoric acid). A ferric ion complex salt may be prepared by reacting ferric iron) with a chelating agent (aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) in a solution. When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be a combination of two or more kinds. The chelating agent may be used in a stoichiometric or higher stoichiometric manner in both cases of forming a complex salt or a complex salt. The bleaching solution or bleach-fixing solution containing the ferric ion complex may contain metal ions other than iron, such as cobalt and copper, and complex salts thereof or hydrogen peroxide.

The persulfate for bleaching or bleach-fixing which can be used in the present invention is an alkali metal persulfate such as potassium persulfate or sodium persulfate, or ammonium persulfate.

The bleaching solution or the bleach-fixing solution may include rehalogenated bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, ammonium iodide). An agent can be included. Boric acid, if necessary
Borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
It is possible to add one or more kinds of inorganic acids and organic acids having a pH buffering ability and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine.

A suitable amount of the bleaching agent per bleaching solution is 0.1 to 2 mol, and a preferable pH range of the bleaching solution is 0.5 to 8.0 in the case of ferric ion complex salt, especially aminopolycarboxylic acid, aminopolyphosphonic acid, In the case of a ferric ion complex salt of phosphonocarboxylic acid or organic phosphonic acid, it is 4.0 to 7.0. In the case of persulfate, the pH is preferably in the range of 1 to 5 at a concentration of 0.1 to 2 mol /.

The fixing agents used for fixing or bleach-fixing are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, 3 It is a water-soluble silver halide solubilizer such as thioether compounds such as 6,6-dithia-1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. In the bleach-fixing process, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used.

In the case of fixing or bleach-fixing, the concentration of the fixing agent is 0.2 to
4 mol / is desirable. In the bleach-fixing process,
It is preferable that the ferric ion complex salt is in the range of 0.1 to 2 mol and the fixing agent is in the range of 0.2 to 4 mol per one bleach-fixing solution. The pH of the fixing and bleach-fixing solution is usually preferably 4.0 to 9.0, and particularly preferably 5.0 to 8.0.

The fixing solution or the bleach-fixing solution contains sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfite, hydroxylamine, hydrazine as preservatives other than the above-mentioned additives that can be added to the bleaching solution. A bisulfite adduct of an aldehyde compound (eg, acetaldehyde sodium bisulfite) and the like can be included. Further, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
988, JP-A-53-32736, JP-A-53-57831, and JP-A-37481.
No. 53, No. 53-65732, No. 53-72623, No. 53-95630,
53-59631, 53-104232, 53-124424, 5
Compounds having a mercapto group or a disulphide group described in 3-141623, 53-28426 and Research Disclosure No. 17129 (July 1978);
Thiazolidine derivatives as described in 140129; JP-B-45-8506, JP-A-52-20832, JP-A-53-32735,
Thiourea derivatives described in U.S. Pat. No. 3,706,561; iodides described in West German Patent 1,127,715 and JP-A-58-16235;
Polyethylene oxides described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B No. 45-8836; other JP-A Nos. 49-42434 and 49-59644;
The compounds described in JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940 can also be used. Among them, a compound having a mercapto group or a disulfide group is preferable in terms of a large accelerating effect,
Especially U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95630 are preferred.

After the fixing step or the bleach-fixing step, the water washing processing step according to the present invention is performed as described above.

In addition, in the case of continuous processing, a constant finish can be obtained by using a replenisher of each processing solution to prevent the composition of the solution from varying. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen agitation, air agitation and the like may be provided in each treatment bath.

(Example) Next, the present invention will be specifically described with reference to Examples.

Reference Example Fuji Color Paper Type 12 was imagewise exposed, and then continuously processed using Fuji Color Roll Processor FFRP115 (manufactured by Fuji Photo Film Co., Ltd.) in the following processing steps.
This processor has a variable treatment time in the water washing step.

In addition, the amount of the processing liquid carried in from the previous tank of each tank from the bleach-fixing step to the water washing is 40 ml / m ³ .

The replenishing amount in the color developing step is 161 ml per 1 m ² of the light-sensitive material, and the solution used is as follows.

The replenishing amount in the bleach-fixing step is 60 ml per 1 m ² of the light-sensitive material. The liquid used has the following formulation.

The amount of replenishing water in the washing step was 10 per 1 m ² of the light-sensitive material.

The processing was carried out by using the above-mentioned photosensitive material having a width of 8.25 cm by 180 m per day for 90 days. Then, various light-sensitive materials were prepared as described below, and the unexposed samples were processed by treating the processors with water as shown in Table 1.

The following first layer (lowermost layer) to seventh layer (uppermost layer) were coated on a paper support laminated on both sides with polyethylene to prepare a multilayer halogen-under-silver color light-sensitive material.

The coating solution for the first layer was prepared as follows. That is, 100 g of the yellow coupler shown in Table 1 was dissolved in a mixed solution of 166.7 ml of dibutyl phthalate (DBP) and 200 ml of ethyl acetate, and this solution was added to 800 g of 10% gelatin aqueous solution containing 80 ml of 1% sodium dodecylbenzenesulfonate aqueous solution.
To 1450 g of a blue-sensitive silver chlorobromide emulsion (Br80%) (containing 66.7 g of Ag) to prepare a coating solution. Coating solutions were prepared for the other layers by the same method. As the hardener for each layer, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was used. At this time, the amount of the hardener added was adjusted so that the swelling degree shown in Table 1 was obtained for each light-sensitive material.

 The following were used as the photosensitizers for each emulsion.

Blue-sensitive emulsion layer; 3,3'-di- (r-sulfopropyl) -selenacyanine sodium salt (2 per mol of silver halide)
× 10 ^-4 mol) Green-sensitive emulsion layer; 3,3'-di- (r-sulfopropyl) -5,
5'-diphenyl-9-ethyloxacarbocyanine sodium salt (2.5 × 10 ^-4 mol per mol of silver halide) Red-sensitive emulsion layer; 3,3'-di- (r-sulfopropyl) -9
-Methyl-thiazicarbocyanine sodium salt (2.5 × 10 ^-4 mol per mol of silver halide) The following dyes were used as irradiation prevention dyes for each emulsion layer.

The chemical structures of the compounds in the above table are as follows.

The structure of the magenta coupler used is as follows.

When the above magenta coupler was used, the amount of silver in the green-sensitive layer was 0.44 g / m ² .

As is clear from the results shown in Table 1, when the swelling degree is smaller than the range of the present invention and the water washing time is set to a short treatment time of 90 seconds or less (No. 1 to 4, 22, 27), immediately after the treatment and with the passage of time. Even if the subsequent yellow stain is high and the degree of swelling is larger than that of the present invention (No. 17 to 20, 26, 31), the yellow stain concentration is also high. Further, when the treatment time is shorter than the water washing treatment time of the present invention, the yellow stain immediately after the treatment and after the passage of time is high even if the swelling degree is within the range of the present invention (No. 9, 17).

As described above, the yellow stain immediately after the treatment and the increase in the yellow stain due to the treatment occurring in the treatment in which the washing treatment time is shortened to 30 to 90 seconds are solved by using the photosensitive material whose swelling degree is within the range of the present invention. I understand that

Further, in the present invention, when the magenta couplers M-5 and m-11 described as preferable in the specification are used (Nos. 23 to 25 and 28 to 30), the yellow color is higher than that when the magenta coupler is used. It can be seen that the stain is less increased with time and is more preferable.

Example 1 The same continuous treatment as in Reference Example was performed except that the washing step was as described below. The replenishment amount after washing with water was 300 ml per 1 m ² of the light-sensitive material, and the washing time was 20 seconds in each tank for a total of 60 seconds. Washing temperature is 30 ° C ±
3 ° C. The formulation of the washing solution is shown below.

Washing water Water 950 ml Benzotriazole 1.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ammonium banban 1.0 g Adjust pH to 7.0 with ammonia water Add water 1000 ml 8.25 cm width A sample prepared in the same manner as in the reference example was treated with the treatment liquid obtained by treating the material 180 m per day for 90 days. Similarly to the reference example, the yellow stain immediately after the treatment and the yellow stain concentration after aging for 8 weeks under the conditions of 60 ° C. and 70% relative humidity were measured. The result is the second
Shown in the table.

As shown in Table 2, even in the processing in which the replenishing amount of washing water is significantly reduced, when a light-sensitive material having a swelling degree within the scope of the present invention is used, as in the case of ordinary washing, immediately after the processing and after the passage of time. It was found that the yellow stain density of the product was low.

On the other hand, it can be seen that the yellow stain concentration is high regardless of whether the degree of swelling is larger or smaller than the range of the present invention (1.5 to 4.0) (No. 32, 36, 37, 41, 42, 46). The present invention is effective even when the replenishment amount of washing water is large, but is particularly effective in water-saving treatment in which the replenishment amount of washing water is small.

Example 2 Another layer color photographic paper having the layer constitution shown in Table A was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (a) and color image stabilizer (b)
To 4.4 g, 27.2 ml of ethyl acetate and 7.9 ml of the solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 80 mol% of silver bromide and 70 g / kg of Ag) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 0 × 10 ⁻⁴ mol.
The emulsified dispersion and the emulsion were mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table A was obtained, and the coating solution for the first layer was prepared. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. Various gelatin hardeners include 1-oxy-3,
5-Dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizer for each emulsion.

The following dyes were used as the anti-irradiation dye in each emulsion layer.

Structural formulas of compounds such as couplers used in this example are as follows.

(E) Magenta coupler M-6 (J) Solvent (iso C ₉ H ₁₈ O ₃ P = O The emulsions used are as shown in Table B below.

The obtained color photographic paper was imagewise exposed, and then Fuji Color Paper Processor PP-600 was modified and processed in the following processing steps. The amount of each treatment was repeated until the amount of each color developing tank was replenished by 3 times.

The carry-in amount of each bath was 35 ml per 1 m ² of the light-sensitive material.

Treatment process Time ^* Temperature Color development 45 seconds 35 ℃ Bleaching fixing 45 seconds 35 ℃ Rinse 20 seconds 35 ℃ Rinse 20 seconds 35 ℃ Rinse 20 seconds 35 ℃ Dry 50 s 80 ℃ (rinse solution is for 3 tanks from rinse to →) The composition of each treatment liquid used is as follows.

However, the replenishment amount of each liquid used is as follows.

Color developer 160ml / m ² Bleach-fixer 100ml / m ² Similar to the color printing paper shown in Tables A and B, the third
Magenta couplers shown in the table and color photographic papers having different degrees of swelling were prepared, exposed to a wedge shape, and subjected to the processing conditions (change of rinse time and rinse replenishment amount) shown in Table 3 using the above running liquid. Processed.

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

Swelling degree Aging condition 1.0 20 ° C 20 hours 1.5 60 ° C 20 hours 2.5 40 ° C 16 hours 3.5 30 ° C 16 hours 4.5 25 ° C 16 hours Yellow stain after 80 days at 80 ° C / 70% RH of each treated color printing paper Concentration, magenta stain concentration after 4 weeks at 80 ℃ and xenon light (85000Lux, distance 50cm) 12
Days fading rate of the magenta density after irradiation results measured at Macbeth densitometer (D _G = 2.0) are shown in Table 3.

 The magenta couplers used are as follows.

From Table 3, when the degree of swelling is smaller than that of the present invention, yellow and magenta stains are large (47R, 55R, 66R, 76R).
If R) is higher than the swelling degree of the present invention, the yellow stain is particularly large, and photobleaching is not preferable.
Furthermore, there were many cases where scratches were generated on the surface of the processed color photographic paper (51R, 62R, 73R). When the replenishment amount of the rinse solution is significantly smaller than the replenishment amount of the water-saving treatment which is usually performed, yellow and magenta stain are generated (52R, 63R, 70R), but from other results, the present invention is used. It can be seen that considerable water saving treatment can be effectively performed.
Also in the present invention, when the replenishment amount of the rinse is extremely large, the photobleaching of magenta is slightly inferior. When the washing time is shorter than that of the present invention, yellow and magenta stain are generated (54R, 57R, 65R, 68R).

The most favorable photographic performance was obtained by processing the magenta coupler of the present invention under the processing conditions of the present invention (60,61,67,69,71,72,75,77).

Example 3 As described in Table C, the first layer (lowermost layer) to the seventh layer (uppermost layer) were applied to a double-sided polyethylene laminated paper that had been subjected to corona discharge processing to prepare a sample.

The coating liquid for the first layer was prepared as follows.
That is, a mixture of 200 g of the yellow coupler shown in Table C, 93.3 g of the anti-fading agent, 10 g of the high boiling point solvents (p) and 5 g of the high boiling point solvent, and 600 ml of ethyl acetate as an auxiliary solvent was dissolved by heating at 60 ° C., and then alkanol B was added. (Alkylnaphthalene sulfonate, manufactured by Dyupon) was mixed with 3300 ml of a 5% gelatin aqueous solution containing 330 ml of a 5% aqueous solution, and the mixture was emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off from this dispersion under reduced pressure, and the sensitizing dye for the blue-sensitive emulsion layer and 1-
Methyl-2-mercapto-5-acetylamino-1,3,4
-Add to 1400 g of emulsion containing triazole (including 96.7 g as Ag and 170 g of gelatin), and further add 10% gelatin aqueous solution.
A coating solution was prepared by adding 2600 g.

The coating solutions for the second to seventh layers were prepared according to the first layer.

n 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole o 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole p di (2-ethylhexyl) phthalate q dibutyl Phthalate r 2,5-di-tert-amylphenyl-3,5-di-tert-
Butylhydroxybenzoate s 2,5-di-tert-octylhydroquinone t 1,4-di-tert-amyl-2,5-dioctyloxybenzene u 2,2′-methylenebis (4-methyl-6-tert-butylphenol In addition, the following substances were used as the sensitizing dye for 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 '-Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9,9'
-(2,2-dimethyl-1,3-propano) thiazicarbocyanine iodide The following compounds were used as stabilizers for each emulsion layer.

1-methyl-2-mercapto-5-acetylamino-1,
3,4-Triazole The following substances were used as the anti-irradiation dye.

4- (3-carboxy-5-hydroxy-4- (3-
(3carboxy-5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl) benzenesulfonate-di-potassium salt N, N '-( 4,8-dihydroxy-9,10-dioxo-3,7-
Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt Also, 1,2-bis (vinylsulfonyl) ethane was used as a hardening agent.

 The respective couplers used are as follows.

After the imagewise exposure of the multi-layer color photographic paper obtained as described above, the FPRP115 made by Fujifilm was remodeled in the following processing steps, and continuous processing was performed until replenishing the color developing tank three times. Treatment process Temperature Time Color development 35 ℃ 45 seconds Bleaching 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 → 1 It was washed with countercurrent water.

The color developers used in the above processing steps are as follows.

The bleach-fix used in the above processing step was the same as in Example 2. As for the rinse solution, the replenisher solution and the tank solution were the same, and the following solutions were used.

Rinse solution 5-chloro-2-methyl-4-isothiazolin-3-one 40 mg 2-Methyl-4-isothiazolin-3-one 10 mg 2-octyl-4-isothiazolin-3-one 10 mg Bismuth chloride (40% Aqueous solution) 0.50 g Nitrilo-N, N, N-trimethylenephosphonic acid (40%) 1.0
ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.5 ml Fluorescent whitening agent (4,4'-diaminostilbene type) 1.0 g Ammonia water (26%) 2 ml Water is added to pH 7.0 color developer, bleach-fix and rinse with 1000 ml KOH. The replenishing amounts of the liquid were 160 ml, 60 ml and 120 ml per 1 m ² of color photographic paper, respectively.

A light-sensitive material in which only the magenta coupler was changed was prepared in the same manner as in Table C, and the light-sensitive material in which the degree of swelling was changed after coating was wedge-shaped exposed in the same manner as in Example 2, and the running solution was prepared. It was used and processed with only the rinse time changed (see Table 4 for details). With respect to the obtained processed light-sensitive material, the stain density after aging and photobleaching with time (however, irradiation with a fluorescent lamp and 3000 Lux at a distance of 30 cm for 4 months) were measured in the same manner as in Example 2. Table 4 shows the results.

As shown in Table 4, when the degree of swelling is smaller than that of the present invention, yellow and magenta stain are large (78R, 79R, 86R, 92R, 98R),
If the degree of swelling is large, the yellow stain is large and the photobleaching of magenta is also deteriorated (84R, 85R, 88R, 94R, 100R).
If the washing time is short, yellow and magenta stains are large. According to the constitution of the present invention, good photographic performance can be obtained, and further excellent performance can be obtained by using the preferable magenta coupler of the present invention (90,91,93,96,97,9).
9).

Example 4 On a paper support laminated on both sides with polyethylene, a multi-layer color photographic paper having a layer constitution shown in Table D with different magenta couplers was prepared. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (a) and color image stabilizer (b)
To 4.4 g, 27.2 ml of ethyl acetate and 7.9 ml of the solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 1.0 mol% of silver bromide and 70 g / kg of Ag) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 0 × 10 ⁻⁴ mol.
The emulsified dispersion and the emulsion were mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table B was obtained, and the coating solution for the first layer was prepared.

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

 The following were used as the spectral sensitizer for each emulsion.

(Addition of 0.9 × 10 ⁻⁴ mol per mol of silver halide) The following dye was used as an anti-irradiation dye in each emulsion layer.

Structural formulas of compounds such as couplers used in this example are as follows.

(J) Solvent (isoC ₉ H ₁₉ O ₃ P = O However, as shown in Table 5, multilayer color photographic papers having swelling degrees of 1.0, 2.0, 4.0 and 5.0 were prepared by changing the amount of the hardener.

The color printing paper obtained as described above was continuously processed in the same processing steps as in Example 4. However, the rinse time was changed as shown in Table 5. Each processing amount was repeated until the tank capacity of the color developing solution was tripled. The treatment liquids used are as follows.

Bleach-fix solution (tank solution and replenisher are the same formulation) EDTA Fe (III) NH ₄・ 2H ₂ O 60 g DETA ・ 2Na ・ 2H ₂ O 4 g Ammonium thiosulfate (70%) 120 ml Sodium sulfite 16 g Glacial acetic acid 7 g Water to add 1000 ml pH 5.5 Rinse solution (tank solution and replenisher have the same formulation) EDTA ・ 2Na ・ 2H ₂ O 0.4 g Water to add 1000 ml pH 7.0 Replenishing amount of each solution per 1 cm ² of color photosensitive material Color developer 160ml Bleach-fix solution 100ml Rinse solution 200ml.

In the same manner as in Example 3, the temporal stain density after treatment and the photobleaching of magenta in each running test were measured.

According to the present invention, not only the increase in yellow stain and magenta stain after treatment is small, but the photobleaching of magenta is also small, whereas the increase of stain is large when the total rinse time is 30 seconds or less, and the swelling also occurs. When the degree exceeds 4, magenta photobleaching is significantly deteriorated.

(Effect of the Invention) According to the present invention, an excellent color image having good stain immediately after processing and after aging can be obtained even when the development processing is carried out with a shortened washing processing time of 30 to 90 seconds.
Further, even if the water-washing treatment is a water-saving treatment, such an excellent color image can be obtained. Furthermore, by using a light-sensitive material containing a specific magenta coupler, an excellent color image having particularly good stain after aging can be obtained.

Claims (2)

(57) [Claims] 1. In the development processing of a silver halide color photographic light-sensitive material, a light-sensitive material having a swelling degree of the photographic layer of 1.5 to 4.0 is treated with a total processing time of 30 to 90 seconds in the water processing step. An image forming method, characterized in that the replenishing amount is 120 to 300 ml / m ² and continuous processing is performed in a countercurrent type of ² to 9 tanks. 2. A silver halide color photographic light-sensitive material containing 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). (In the formula, R ₁ represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer, and Z _a , Z _b , and
Z _c represents methine, substituted methine, = N- or -NH-, and one of the Z _a -Z _b bond and the Z _b -Z _c bond is a double bond and the other is a single bond. When Z _b -Z _c is a carbon-carbon double bond, it includes a case where it is a part of an aromatic ring, and further includes a case where R ₁ or X forms a dimer or higher multimer, and , Z _a , Z _b , or Z _c is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer. ) (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 unsubstituted acylamino group, ureido group or anilino group.)