JPH0934072A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material good in gradation balance in the case of ordinary color development processing and also rapid development processing and superior in tone and color reproduction performances by incorporating a specified coupler in a green-sensitive silver halide emulsion layer and allowing the gradation of each color obtained at the time of executing development processings different from each other in color developing time to satisfy specified conditions. SOLUTION: The photosensitive material containing a coupler represented by formula I in the green-sensitive silver halide emulsion layer and also containing a basic metal compound hardly soluble in water, in subjected to the development processings I and II different from each other in the color developing time to obtain cyan, magenta, and yellow of which gradation satisfy the conditions represented by expressions II. In formula I, R1 is an alkyl group or the like; Ar is a phenyl group or the like; and X is a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent and to combine with the 4-position of a pyrazolone ring through an ioized atom. In expression II, γI(Y), γI(M), and γI(C) and γII(Y), γII(M), and γII(C) are the gradations of yellow, magenta, and cyan at the time of being subjected to the development processings I and II, respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an image forming method for a silver halide color photographic light-sensitive material, and
Even if the current color negative development process and the rapid development process of the color development are carried out with improved magenta color development ability, the gradations of magenta color images obtained by both processes can be obtained to the same degree, and three colors of cyan, magenta and yellow are obtained. The present invention relates to a silver halide color photographic light-sensitive material excellent in tone balance, tone reproduction and color reproducibility.

[0002]

2. Description of the Related Art In recent years, with respect to color development processing of color photographic light-sensitive materials, research and development for shortening the processing time have been earnestly conducted. Regarding the color negative development processing, the speeding up of the conventional processing is mainly achieved by shortening the processing time of the desilvering step. For example, in the quick processing CN-16FA of Fuji Photo Film Co., Ltd., which was introduced for the minilab market, the processing time was reduced to 8 minutes and 15 seconds. However, in this processing, the color development time accounts for 40% of the total processing time. Therefore, the introduction of rapid processing that shortens the color development time is a major problem in this industry. Many proposals have been made for solving this problem. However, by simply applying high temperature processing of color development, high pH processing of developing solution, high concentration processing of color developing agent, improvement of film quality of photosensitive material, thinning of photosensitive material constituting layer or combination thereof, it is shortened from the present Even if the processing is carried out for the above-mentioned color development time, the gradation balance of the three colors of cyan, magenta and yellow, which are the most important as a color negative, is greatly disturbed, and the cyan color of the red-sensitive layer coated on the side closer to the support is not colored. Be late. In order to solve the problem of the delay in cyan color development, there is a proposal to incorporate a poorly water-soluble basic metal compound into a layer near the support to promote color development. Although this proposal is certainly effective, depending on the magenta coupler used for the green-sensitive layer,
It became clear that another problem that magenta color development was adversely affected and color development inhibition occurred was derived, and there was an urgent need to solve this problem.

On the other hand, regarding the use of a poorly water-soluble basic metal compound as a light-sensitive material, for example, JP-A-63-01194 is used.
No. 0 (Document 1), the use of the metal compound and a color developing treatment using a processing solution containing a complex-forming compound that causes a complex-forming reaction with respect to the metal ions constituting the metal compound to release a base. Is also described, and specific examples of magenta couplers used for light-sensitive materials are also presented. Although some of these magenta couplers specifically described in this document 1 are described as couplers that are not easily affected by the inhibition of magenta color development, different color development times are obtained using these couplers. Cyan obtained from both types of processing when two types of processing, for example, the current color negative processing and the rapid processing with shortened color development time, are carried out,
It is the current situation that a processing method is not yet achieved in which the gradations of the three colors of magenta and yellow are both balanced and the photographic performance of the same gradation is obtained. In this way, the same color sensitive material is used, and different color development times are used.
It is more preferable that an image forming method capable of obtaining photographic performance of the same gradation even if various kinds of processing are carried out, especially if one of the processings is an image forming method by a quicker processing than the current one, and there is a strong demand in the industry for its appearance. In JP-A-3-017648 (Reference 2), a compound which also contains a poorly water-soluble basic metal compound in a light-sensitive material and releases a base when complexed with a metal ion constituting the metal compound It is described to process with a color developing solution containing There is also a description relating to magenta couplers. However, in Reference 2, the composition of the silver halide used in the light-sensitive material is substantially free of silver iodide, and is the use of silver halide containing 80 mol% or more of silver chloride, which is substantially the present invention. The color developing solution containing the compound that releases the base is an image forming method applied in a thin layer on the surface of the light-sensitive material, and is different from the image forming method according to the present invention. It is a thing.

[0004]

Therefore, the present invention provides a color-sensitive material having at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and at least one light-insensitive layer on a support, and a green-sensitive halogenogen. General formula (m) for silver halide emulsion layer
When a coupler represented by the formula (1) and a photosensitive material containing at least one layer containing a sparingly water-soluble basic metal compound are subjected to two kinds of development treatments with different color development times, three colors of cyan, magenta and yellow are obtained. Provided is an image forming method of a silver halide color photographic light-sensitive material, which has a good gradation balance of three colors and excellent tone reproduction and color reproducibility by a color development process in which the gradation degree of 3 satisfies a specific conditional expression. The purpose is to

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made a method for forming an image of a color light-sensitive material which has a good gradation balance of the three colors of cyan, magenta and yellow and is excellent in tone reproduction and color reproducibility. Are at least one red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layer and a non-photosensitive layer on the support.
Using a specific magenta coupler represented by the general formula (m) in the green-sensitive silver halide emulsion layer of the color light-sensitive material having layers,
A color light-sensitive material containing a basic metal compound that is poorly water-soluble in at least one layer is treated with two types of treatments with different color development times, one treatment according to the current color negative treatment, and the other treatment with color development. The present invention has been completed by finding a color light-sensitive material which achieves the above-mentioned object when the gradation degree obtained from both the processes satisfies the specific conditional expression even if the rapid process which shortens the time is carried out. That is, the present invention

(1) A silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer and non-photosensitive layer on a support. A silver halide containing a coupler represented by the general formula (m) in the green-sensitive silver halide emulsion layer of the photographic light-sensitive material, and at least one layer containing a poorly water-soluble basic metal compound. When a color photographic light-sensitive material is subjected to the following two types of development processing (I) and development processing (II) with different color development times,
A silver halide color photographic light-sensitive material characterized in that the gradations of cyan, magenta and yellow obtained by the two types of development processes satisfy the following conditional expressions. General formula (m)

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(Wherein R ₁ is an alkyl group, an aryl group,
Represents an acyl group or a carbamoyl group, and Ar is substituted with a phenyl group or one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, a sulfonyl group or a sulfamoyl group. Represents a phenyl group, and X represents a group which can be released by a coupling reaction with an oxidation product of an aromatic primary amine developing agent and which is bonded to the 4-position of the pyrazolone skeleton with a sulfur atom. ) Conditional expression 0.8 ≦ γ _II (Y) / γ _I (Y) ≦ 1.2 0.8 ≦ γ _II (M) / γ _I (M) ≦ 1.2 0.8 ≦ γ _II (C) / Γ _I (C) ≦ 1.2 (γ _I (Y), γ _I (M), γ _I (C) respectively represent the gradation levels of yellow, magenta, and cyan when the development processing I is carried out, and γ _II (Y), γ _II (M), γ _II (C)
Represents the gradation levels of yellow, magenta, and cyan when the development processing II was carried out. (Development Treatment I) Color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N-as a color developing agent. (Β-
A development process characterized in that the color development process is performed using a color development solution containing 15 to 20 mmol / L of hydroxyethyl) amino] aniline. (Development Treatment II) Color development time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N- (β-hydroxy) is used as a color developing agent. 35-40 mmol of ethyl) amino] aniline /
A developing treatment, characterized in that the color developing treatment is carried out using a color developing solution containing a compound which promotes the release of a base from a basic metal compound having a solubility in water and a poorly water-soluble basic metal compound.

(2) The halogen according to (1), wherein the photographic light-sensitive material has a magnetic layer containing a ferromagnetic powder in the back layer on the side opposite to the side of the photosensitive emulsion layer with the support interposed therebetween. Silver halide color photographic light-sensitive material.

(3) A color image forming method characterized in that a color image is formed by carrying out the following development processing A using the silver halide color photographic light-sensitive material described in (1) or (2). . (Development treatment A) The color developing time is 150 to 200 seconds, the temperature of the color developing solution is 37 to 40 ° C., and a color developing solution containing 15 to 20 mmol / liter of a color developing agent is used. Development process.

(4) A color image forming method characterized in that a color image is formed by carrying out the following development processing B using the silver halide color photographic light-sensitive material described in (1) or (2). .. (Development treatment B) Color development time is 25 to 90 seconds, temperature of color developing solution is 40 to 60 ° C., concentration of color developing agent is 25 to 80 mmol / liter, and basic metal compound hardly soluble in water is used. A development process comprising using a color developing solution containing a compound that accelerates the release of a base.

In the above aspect (1), a red-sensitive material is provided on the support,
A magenta coupler represented by the general formula (m) is contained in the green-sensitive silver halide emulsion layer of a color light-sensitive material having at least one green-sensitive and blue-sensitive silver halide emulsion layer and at least one light-insensitive layer, and at least the above When two kinds of color sensitive materials each containing a poorly water-soluble basic metal compound in one layer are subjected to two kinds of developing treatments having different color development times, the gradations of cyan, magenta and yellow obtained from the both treatments meet specific conditions. When the formula is satisfied, it is an image forming method of a silver halide color photographic light-sensitive material which does not inhibit magenta color development, has a good gradation balance of three colors of cyan, magenta and yellow and is excellent in tone reproducibility and color reproducibility. The technology relating to the image forming method of such a color sensitive material is a technology which has not been disclosed so far, which defines a magenta coupler used in a green sensitive emulsion layer and which is a poorly water-soluble basic metal compound. When two kinds of specific developing processes are specified for the color sensitive material using, the tone reproduction of the three colors of cyan, magenta, and yellow obtained from both processes satisfies a specific conditional expression, and good tone reproducibility is obtained. And color reproducibility to achieve the object of the present invention.

A preferred mode (2) is an image forming method of a color light-sensitive material having a magnetic layer containing a ferromagnetic powder in the back layer of the color light-sensitive material of the mode (1), which is a color light-sensitive material having a magnetic layer. Even if there is, the above-mentioned subject of the present invention is achieved.

Aspects (3) and (4) are different from the aspect (1) in that the two types of developing treatments having different color development times are defined separately, and magenta obtained by carrying out these two types of developing treatments. This is an image forming method which does not have a density difference in color images and which conforms to a conditional expression defining gradations of three colors of cyan, magenta and yellow, and the object of the present invention is achieved by these image forming methods.

The present invention will be described below in detail.

First, the coupler of the present invention will be described in detail. In the general formula (m), R ₁ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group, and more specifically, an alkyl group (preferably a linear or branched alkyl group having 1 to 32 carbon atoms, for example, , Methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1
-Octyl, tridecyl), a cycloalkyl group (preferably a cycloalkyl group having 3 to 8 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an aryl group (preferably having 6 carbon atoms) 32 aryl groups, for example, phenyl, 1-naphthyl, 2-naphthyl), acyl groups (preferably acyl groups having 1 to 32 carbon atoms, for example, formyl,
Acetyl, pivaloyl, benzoyl, tetradecanoyl), or carbamoyl group (preferably having 1 to 3 carbon atoms).
A carbamoyl group of 2, for example, carbamoyl, N, N
-Dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl). R ₁
The group represented by may further have a substituent, and as the substituent of R _1, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having a carbon number of 1 to 3)
A linear or branched alkyl group of 2, for example, methyl, ethyl, propyl, isopropyl, butyl, t-
Butyl, 1-octyl, tridecyl), cycloalkyl group (preferably cycloalkyl group having 3 to 8 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl group (preferably having carbon number) 2 to 32 alkenyl groups such as vinyl, allyl, 3-buten-1-yl), aryl groups (preferably aryl groups having 6 to 32 carbon atoms such as phenyl, 1-naphthyl, 2-naphthyl), Heterocyclic group (preferably a 5- to 8-membered heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2
-Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, silyl group (preferably silyl group having 3 to 32 carbon atoms, for example, trimethylsilyl, triethylsilyl, tosibutylsilyl, t- Butyldimethylsilyl, t-hexyldimethylsilyl), nitro group,

Hydroxyl group, alkoxy group (preferably alkoxy group having 1 to 32 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy), cycloalkyloxy group. (Preferably a cycloalkyloxy group having 3 to 8 carbon atoms, for example, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 32 carbon atoms, for example, phenoxy, 2-naphthoxy), Heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), silyloxy group (preferably having carbon number) 1-32 silyloxy groups, for example, trimethylsilyl Xy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 32 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably Is an alkoxycarbonyloxy group having 2 to 32 carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy), cycloalkyloxycarbonyloxy (preferably a cycloalkyloxycarbonyloxy group having 4 to 9 carbon atoms, for example, Cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, for example, phenoxycarbonyloxy), carbamoyloxy group. Group (preferably carbamoyloxy group having 1 to 32 carbon atoms, for example,
N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, for example, N, N-diethylsulfamoyloxy, N- Propylsulfamoyloxy), an alkanesulfonyloxy group (preferably an alkanecarbonyloxy group having 1 to 32 carbon atoms, for example, methanesulfonyloxy, hexadecanesulfonyloxy), arenesulfonyloxy (preferably an arene having 6 to 32 carbon atoms) A sulfonyloxy group, for example, benzenesulfonyloxy),

Acyl group (preferably an acyl group having 1 to 32 carbon atoms, such as formyl, acetyl, pivaloyl,
Benzoyl, tetradecanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl), a cycloalkyloxycarbonyl group (preferably having 2 to 32 carbon atoms). A cycloalkyloxycarbonyl group of, for example, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, for example,
Phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 32 carbon atoms, for example, carbamoyl, N, N-dibutylcarbamoyl, N-ethyl-N).
-Octylcarbamoyl, N-propylcarbamoyl),

Amino group (preferably an amino group having 32 or less carbon atoms, for example, amino, methylamino, N, N-dioctylamino, tetradecylamino, octadecylamino), anilino group (preferably having 6 to 32 carbon atoms). Anilino group, for example, anilino, N-methylanilino),
Heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, for example, 4-pyridylamino), carbonamido group (preferably a carbonamido group having 2 to 32 carbon atoms, for example, acetamide, benzamide, tetradecane). Amido), ureido group (preferably having 1 to 3 carbon atoms)
2 ureido groups, for example, ureido, N, N-dimethylureido, N-phenylureido), imide groups (preferably imide groups having 10 or less carbon atoms, for example, N-succinimide, N-phthalimide), alkoxycarbonyl Amino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino), an aryloxycarbonylamino group (preferably having 7 carbon atoms)
To 32 aryloxycarbonylamino groups such as phenoxycarbonylamino), sulfonamide groups (preferably C1 to C32 sulfonamide groups such as methanesulfonamide, butanesulfonamide,
Benzenesulfonamide, hexadecanesulfonamide), sulfamoylamino group (preferably having 1 to 1 carbon atoms)
32 sulfamoylamino groups, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino, an azo group (preferably an azo group having 1 to 32 carbon atoms, for example, , Phenylazo, 4-methoxyphenylazo),

Alkylthio group (preferably having 1 to 3 carbon atoms)
2 alkylthio groups such as ethylthio and octylthio, arylthio groups (preferably arylthio groups having 6 to 32 carbon atoms such as phenylthio), heterocyclic thio groups (preferably heterocyclic thio groups having 1 to 32 carbon atoms). And, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, for example, dodecanesulfinyl), arenesulfinyl (preferably An arene sulfinyl group having 6 to 32 carbon atoms, for example, benzenesulfinyl),
Alkanesulfonyl group (preferably an alkanesulfonyl group having 1 to 32 carbon atoms, for example, methanesulfonyl, octanesulfonyl), arenesulfonyl group (preferably an arenesulfonyl group having 6 to 32 carbon atoms, for example,
Benzenesulfonyl, 1-naphthalenesulfonyl), sulfamoyl group (preferably sulfamoyl group having 32 or less carbon atoms, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), sulfo group A phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (diethoxyphosphinoylamino, dioctyloxyphosphinoyl) Amino group).

More preferable substituents of the group represented by R ₁ are a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carbamoyl group, a carbonamido group, an alkoxycarbonylamino group and an aryloxy group. A carbonylamino group, a ureido group, a sulfonamide group, an imide group, an alkanesulfonyl group, an arenesulfonyl group, a phosphonyl group and a phosphinoylamino group.

Ar is substituted with a phenyl group having 1 to 32 carbon atoms or one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, a sulfonyl group or a sulfamoyl group. Represents a phenyl group, for example, phenyl, 2,4,6-trichlorophenyl, 2,5-dichlorophenyl, 2,4-dimethyl-6-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6
-Dichloro-4-ethoxycarbonylphenyl, 2,6
-Dichloro-4-cyanophenyl, 2,3,4,5-tetrachlorophenyl, pentachlorophenyl, pentafluorophenyl, 2,3,5,6-tetrachloro-4-
Cyanophenyl, 4-ethoxycarbonyl-2,3
5,6-Tetrachlorophenyl, 4- [2- (2,4-
Di-t-amylphenoxy) butanamide] phenyl. The group represented by Ar may further have a substituent, and preferable substituents are the same as those listed as the substituents of the group represented by R ₁ .

X represents a group bonded to the 4-position of the pyrazolone skeleton with a sulfur atom, which can be released by a coupling reaction with an oxidized product of an aromatic primary amine developing agent.
Alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms, for example, dodecylthio, tetradecylthio,
Hexadecylthio, octadecylthio, tetradecanecarboxylic acid-2-thio), an arylthio group (preferably an arylthio group having 6 to 32 carbon atoms, for example, 2-butoxy-5- (1,1,3,3-tetramethyl-1) -Butyl) phenylthio, 2-pivaloylaminophenylthio, 2-phenoxycarbonylaminophenylthio, 2
-Tetradecanamido phenylthio, 2- (2-octyloxybenzamido) phenylthio, 2- [2-
(2,4-di-t-amylphenoxy) butanamide]
Phenylthio, 4- [2- (2,4-di-t-amylphenoxy) butanamido] phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms,
For example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio) is represented. The group represented by X may further have a substituent, and preferable substituents are the same as those listed as the substituents of the group represented by R ₁ .

The preferred range of the compound of the present invention will be described below. R ₁ is preferably an aryl group or an acyl group, and particularly preferably an aryl group. Ar is preferably a phenyl group substituted with one or more halogen atoms, a cyano group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, a sulfonyl group or a sulfamoyl group, and a halogen atom, a cyano group, an alkoxycarbonyl group, a sulfonyl group or More preferred is a phenyl group substituted with a sulfamoyl group. X is preferably an arylthio group.

5 represented by the general formula (m) of the present invention is described below.
Specific examples of the pyrazolone magenta coupler are shown below, but the present invention is not limited thereto.

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[0027]

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[0028]

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[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

[Chemical 12]

[0036]

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[0037]

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The amount of the coupler represented by formula (m) of the present invention added to the silver halide color photographic light-sensitive material is 3 × 1.
0 ^{−5 to} 3 × 10 ⁻³ mol / m ² , preferably 3 × 10 ⁻⁴
˜2 × 10 ⁻³ mol / m ² and 1 × 10 ⁻⁴ ˜1.5 × 10
^-3 mol / m ² is more preferred. When the green-sensitive emulsion layer is composed of a plurality of layers, the same coupler may be used in these layers, or different couplers may be selectively used.
Further, a plurality of couplers may be mixed and used. The coupler of the present invention can be used in a photosensitive layer or a non-photosensitive layer other than the green-sensitive layer depending on the purpose, but at least one of the couplers of the present invention is used in at least one of the green-sensitive layers. . It can also be used with couplers other than the present invention.

The coupler represented by the general formula (m) of the present invention is disclosed in JP-A-50-122935, US Pat.
No. 3,319, No. 4,876,182, No. 4,9
No. 00,657, No. 5,350,667, European Published Patent No. 0348135, No. 0510576.
No. 06228868, Tokuhyo 6-501786
No. 6-501787 and the like.

The use of the magenta coupler represented by the general formula (m) of the present invention in the green-sensitive layer significantly reduces the inhibition of magenta color development which occurs when a poorly water-soluble basic metal compound described below is used as a sensitive material. It exhibits good color development performance. As a result, color development with different development times
Even if various types of development processes are performed, the gradation of the obtained magenta color image satisfies the range of the specified conditional expression, and the gradations of cyan and yellow also satisfy the specific conditional expression. . As a result, the gradation balance of the three colors is good, and the effects of tone reproduction and color reproduction are excellent, and the object of the present invention is achieved.

Next, the poorly water-soluble basic metal compound will be described.

In the present invention, as an example of the water-insoluble basic metal compound contained in the light-sensitive material, the solubility in water at 20 ° C. (the number of grams of the substance dissolved in 100 g of water)
There preferably those represented by the formula T _m X _n 0.5 or less. Where T is a transition metal such as Zn, Ni, Co, Fe, Mn, Cu, Al, S
n, Sb, Bi, etc., alkaline earth metals such as Ca, B
a, Sr, Mg, etc., wherein X is a counter ion of M that appears in the description of the complex-forming compound described below in water and exhibits alkalinity, for example, carbonate ion, phosphate ion , Silicate ion, borate ion, aluminate ion, hydroxy ion, and oxygen atom.
m and n each represent an integer such that the valences of T and X are balanced.

Preferred specific examples are listed below. Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (CO ₃ ) ₂ ), magnesium oxide, zinc oxide,
Tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide,
Manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate,
Basic zinc carbonate _{(2ZnCO 3 · 3Zn (OH)} 2 · H 2
O), basic magnesium carbonate (3MgCO ₃ · Mg
_{(OH) 2 · 3H 2 O} ), basic nickel carbonate (NiCO
_{3 · 2Ni (OH) 2)} , basic bismuth carbonate (Bi ₂ (
CO ₃ ) O ₂ · H ₂ O), basic cobalt carbonate (2Co
CO ₃ .3Co (OH) ₂ ), aluminum magnesium oxide, copper hydroxide, basic copper carbonate and the like. Of these compounds, those that are not colored are particularly preferred.

The position at which the poorly water-soluble basic metal compound of the present invention is added to the light-sensitive material is an emulsion layer / non-light-sensitive layer (intermediate layer /
Any layer (protective layer, antihalation layer, white pigment layer, etc.) may be used, but a layer closer to the support is preferable. That is, it is preferably added to the non-photosensitive layer located between the emulsion layer closest to the support and the support or to the non-photosensitive intermediate layer adjacent to the emulsion layer in the emulsion layer closest to the support.
Of these, the most preferred addition position is in the non-photosensitive layer located between the emulsion layer closest to the support and the support. Further, it may be contained in only one layer, or may be contained in two or more layers.

The compound (trigger compound) for promoting the release of the base from the poorly water-soluble basic metal compound used in the color developing solution of the present invention will be described below.

The trigger compound of the present invention has a stability constant of log with that of the metal ion constituting the basic metal compound.
It is preferably a complex-forming compound that forms a complex salt having a value of K of 1 or more. For these complex-forming compounds,
For example, A. Martell, R. Smith (AE
Martell, RMSmith), “Critical Stability Constants,”
1-5 ", Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, anilinecarboxylic acids, pyridinecarboxylic acids, aminophosphoric acids, carboxylic acids (mono, Di, tri, tetracarboxylic acids and compounds having substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio and phosphino), alkali metals such as hydroxamic acids, polyacrylates, polyphosphoric acids, guanidine And salts such as amidines and quaternary ammonium salts.

As a preferred specific example, picolinic acid, 5
-Ethylpicolinic acid, 2,3-pyridinedicarboxylic acid,
2,4-pyridinedicarboxylic acid, 5-ethoxycarbonylpicolinic acid, 2,6-pyridinedicarboxylic acid, 2,5
-Pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid,
2-pyridylacetic acid, oxalic acid, citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA, NTA,
CDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, 2,3-pyrazinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, glycine, alanine, glutamic acid,

[0048]

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Alkali metal salts such as guanidine salts,
Examples thereof include salts of amidines and quaternary ammonium salts. Of these, an aromatic heterocyclic compound having at least one —CO ₂ M and one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -C
The position at which O ₂ M is bonded to the ring is particularly preferably the α position with respect to the N atom. M is any of alkali metal, guanidine, amidine and quaternary ammonium ions. More preferred compounds include those represented by the following formula.

[0050]

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In the above formula, R is any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, --CO ₂ M, a hydroxycarbonyl group, and an electron donating group such as an amino group, a substituted amino group and an alkyl group. Represents
Two Rs may be the same or different. Z ₁ and Z
₂ is the same as the definition in R, and Z ₁
And Z ₂ may combine to form a ring fused to a pyridine ring.

The most preferable examples of combinations of a water-insoluble basic metal compound and a complex-forming compound are listed below (wherein M ⁺ is an alkali metal ion, a substituted or unsubstituted guanidinium ion, or an amidinium ion). Or 4
Represents a secondary ammonium ion).

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

[Chemical 21]

[0058]

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These combinations may be used alone or in combination of two or more. Here, the mechanism of generating a base in the film of the photosensitive material in the present invention will be described by taking a combination of potassium picolinate and zinc hydroxide as an example. The reaction of both is shown by the following formula, for example.

[0060]

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That is, when water in the treatment liquid is involved, the picolinate ion causes a complex forming reaction with the zinc ion, and the reaction represented by the above formula proceeds, resulting in the generation of a base. The progress of this reaction is due to the stability of the complex formed, but the stability of the complex represented by ML, ML ₂ and ML ₃ formed from picolinate ion (L ⁻ ) and zinc ion (M ⁺ ) The constants are very large as shown below and well explain the progress of this reaction.

[0062]

[Table 1]

Basic metal compounds which are poorly soluble in water are disclosed in JP-A-59 / 1984.
It is desirable to contain the fine particle dispersion prepared by the method described in JP-A-174830, JP-A-53-102733, etc., and the average particle size thereof is preferably 50 μm or less, particularly preferably 5 μm or less. The addition amount varies depending on the type of treatment liquid, pH, complex formation compound species, compound species of basic metal compound, particle size, treatment temperature, etc., but cannot be specified unconditionally,
0.1 to 200 mmol / m ² , preferably 1 to 50 mmol / m ²
It is good to set the degree. The addition amount of the complex-forming compound contained in the treatment liquid varies depending on the kind of treatment liquid, pH, kind of complex-forming compound and the like, but is generally about 0.01 to 5 mol / liter. The complex-forming compound is contained in the treatment liquid before treatment, but may be contained in the replenisher.

The gradation degree in the present invention is obtained as follows. First, the test light-sensitive material is wedge-exposed with a light source having an energy distribution of black body radiation of 4800 K °,
After performing the designated development processing, the absorption densities of cyan, magenta, and yellow are measured under the status M condition, and the characteristic curve is obtained. From the obtained characteristic curve, the absorption densities of cyan, magenta, and yellow are fog +0.2, +0.5, +1.0, +1.5, + with respect to the logarithm of the exposure amount (horizontal axis).
After plotting the points of 2.0 respectively and linearly approximating these points by the method of least squares, tan with respect to the angle θ from the horizontal axis
θ is defined as the gradation degree γ of the photosensitive material, and γ of cyan, magenta, and yellow are γ (C), γ (M), and γ, respectively.
(Y).

The light-sensitive material of the present invention is processed by the development processing I of the present invention.
Gradients γ _I (C), γ _I (M), and γ _I (Y) of cyan, magenta, and yellow after carrying out, and the gradation γ _II (C) after carrying out the developing treatment II of the present invention. , Γ _II (M),
γ _II (Y) satisfies the following conditional expression. 0.8 ≦ γ _II (C) / γ _I (C) ≦ 1.2 0.8 ≦ γ _II (M) / γ _I (M) ≦ 1.2 0.8 ≦ γ _II (Y) / γ _I (Y) ≦ 1.2

More preferably 0.9 ≦ γ _II (C) / γ _I (C) ≦ 1.1 0.9 ≦ γ _II (M) / γ _I (M) ≦ 1.1 0.9 ≦ γ _II It satisfies the condition of (Y) / γ _I (Y) ≦ 1.1.

If this condition is not satisfied, the tint of the print obtained from the color negative developed in at least one of the developing processes A and B will be lost, and it will not be possible to obtain color reproduction that is enduring to the eye.

In the present invention, γ _I (C), γ
_I (M), γ _I (Y), γ _II (C), γ _II (M), γ _II
(Y) is preferably 0.50 to 0.90, more preferably 0.60 to 0.85,
It is particularly preferably 0.65 to 0.80.

The color developing solutions of the developing treatments I and II of the present invention will be described below. The development processing I of the present invention is a processing based on Kodak C-41 which is a processing for color negative which is widely used in the world at present.
It is designed so that a preferable gradation can be obtained in seconds. Further, the development processing II is a processing in which the development processing I is speeded up, and the development activity is increased by increasing the concentration of the main agent and the processing temperature.
It is designed so that a gradation close to that of the development processing I can be obtained in a color development processing time of a minute. However, when a light-sensitive material which is not included in the present invention is processed, development delay occurs in the red-sensitive layer, which is the lowermost layer, so that the gradation cannot be perfectly adjusted.

In the development processing I, the color development time is from 3 minutes to 3 minutes 1
5 seconds, the temperature of the color developing solution is 37 to 39 ° C.,
2-Methyl-4- [N-ethyl-N as color developing agent
15- (β-hydroxyethyl) amino] aniline
This is a developing process characterized by carrying out a color developing process using a color developing solution containing 20 mmol / liter.

In the developing treatment II, the color developing time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N-as a color developing agent is used.
(Β-hydroxyethyl) amino] aniline 35-4
This is a developing treatment characterized by performing a color developing treatment using a color developing solution containing 0 mmol / liter of a compound (trigger compound) which accelerates release of a base from a poorly water-soluble basic metal compound. The trigger compound added to the color developing solution of the development processing II can be selected according to the kind of the base releasing agent added to the light-sensitive material, and the addition amount is 0.02 to 0.5.
The range is preferably mol / liter, more preferably 0.05 to 0.3 mol / liter.

The pH of the color developing solutions used in development processing I and II is 1
It is 0.05. It is preferable to use a carbonate in order to keep the pH of the treatment liquid at 10.05. The addition amount is preferably 0.1 mol / liter or more, and particularly preferably in the range of 0.2 mol / liter to 0.3 mol / liter.
Further, as a preservative for the color developing agent, it is preferable to use hydroxylamine and sulfite. The addition amount of hydroxylamine is preferably in the range of 0.05 mol / liter to 0.2 mol / liter. The amount of sulfite added is 0.
The range of 02 mol / liter to 0.04 mol / liter is preferable. Bromide ions can be added to the color developing solution in order to control the developing rate. Further, various chelating agents can be added to the color developing solution.

The steps (desilvering step, washing step, stabilizing step) subsequent to the color development in the development processings I and II are carried out by the methods described in the development processings A and B described later.

Specific examples of the development processing I and the development processing II are shown below. In the present invention, it is preferable to use the following specific examples. Specific Example of Development Treatment (I) The development treatment in which the color development has the following liquid composition, temperature, and processing time. (Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1 0.5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (with potassium hydroxide Adjusted with sulfuric acid) 10.05 Temperature 38 ° C. Processing time 3 minutes 15 seconds Specific example of development processing (II) Color development is the following liquid composition, temperature and processing time. (Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2.0 Potassium iodide 1 .3 mg Hydroxylamine sulfate 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Picolinic acid 12.0 Water was added to 1.0 liter pH (Adjust with potassium hydroxide and sulfuric acid) 10.05 Temperature 45 ° C Treatment time 60 seconds

To the color development processing solution of the present invention, a substance which promotes release of a base from the poorly water-soluble basic metal compound of the present invention contained in a light-sensitive material can be added. These additives are the trigger compounds mentioned in the above description. Specifically, it is a complex-forming compound that forms a complex salt with a metal ion constituting the basic metal compound, and particularly preferred are picolinic acid, pyridine-2,6-dicarboxylic acid, and pyridine-2,5. -Dicarboxylic acid, 5-ethylpicolinic acid, 5-methylpicolinic acid,
Oxalic acid is an example. However, these trigger compounds are not limited to the above specific examples, because the preferable combination changes depending on the kind of the hardly soluble basic metal salt contained in the photosensitive material.

Note that picolinic acid is added to the color developer of the development processing II as a compound that promotes the release of a base from a poorly water-soluble basic metal compound, but the compound that promotes is not limited to picolinic acid. Instead, it can be selected according to the type of basic metal compound.

Next, development processing A and development processing B of the present invention
Will be described in detail. The development processing A and the development processing B of the present invention each include a color development step, a desilvering step, and a drying step. Specific preferred examples are shown below, but the invention is not limited thereto. Color development-bleach-fix-wash-stable-dry Color development-bleach-bleach-fix-fix-wash-stable-dry Color development-bleach-fix-wash-stable-dry Color-bleach-bleach-fix-wash-stable- Drying Color development-bleach-fixing-fixing-washing-stabilization-drying Color development-bleaching-washing-fixing-washing-stability-drying In the above processing step, washing in the step before stabilization can be omitted. The final stability can also be omitted. In the development processing A and the development processing B of the present invention, the desilvering step of the color development processing may be the same or different.

The color development processing A in the development processing A of the present invention will be described in detail below. The color development time of the color development processing A of the present invention is 150 seconds or more and 200 seconds or less, preferably 165 seconds or more and 195 seconds or less. The color development time can be changed depending on the type and concentration of the developing agent in the processing liquid, the halogen ion (particularly Br ⁻ ) concentration, the temperature of the processing liquid, the pH and the like.

The developing agent in color development processing A of the present invention is 2
-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] alinine, 2-methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl- 4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline is preferred, and 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline is particularly preferred. The concentration of the developing agent is 15 mmol or more and 20 mmol or less, preferably 15 mol mil or more and 18 mmol or less, per liter of the processing liquid. These developing agents are preferably hydrochloride, p-toluenesulfonate or sulfate.

[0080] Bromide ion concentration, Br from a silver halide color photographic material ^- and elution, Br is replenished in the color developing solution ^- is determined by the amount, to keep the photographic properties during continuous processing stably The amount is 6 mmol or more and 14 mmol or less, preferably 9 mmol or more and 13 mmol or less, per liter of the treatment liquid.

The temperature of the treatment liquid is 37 ° C. or higher and 40 ° C. or lower, preferably 37 ° C. or higher and 39 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 10.3 or less, preferably 10.0 or more and 10.2 or less.

Specifically, a color negative film processing agent, CN-16 or CN-1 manufactured by Fuji Photo Film Co., Ltd.
6X, CN-16Q, CN-16FA color developing solution and color developing replenishing solution, or color negative film processing agent C-41, C-41B manufactured by Eastman Kodak Company,
A color developing solution of C-41RA can be preferably used.

The color development processing B in the development processing B of the present invention will be described below. The color development time of the color development treatment B of the present invention is 25 seconds or more and 90 seconds or less, preferably 35 seconds or more and 75 seconds or less, and most preferably 45 seconds or more 6
5 seconds or less.

The color development time of the present invention is a time including the crossover time (the time from the exit of the color development solution to the processing solution of the next step), and the shorter the crossover time is, the more preferable. From the viewpoint of the performance of the processing equipment, 2 seconds or more and 10 seconds or less are preferable, and 3 seconds or more and 7 seconds or less are more preferable.

The color developing time can be changed in the same manner as in the color developing treatment A depending on the type and concentration of the developing agent in the processing solution, the halogen ion (particularly Br ⁻ ) concentration, the temperature and pH of the processing solution.

The developing agent in color development processing B of the present invention is p
-Phenylenediamine derivatives, preferable representative examples of which are shown below. (D-1) 2-methyl-4- [N-ethyl-N- (β
-Hydroxyethyl) amino] aniline (D-2) 2-methyl-4- [N-ethyl-N- (3
-Hydroxypropyl) amino] aniline (D-3) 2-methyl-4- [N-ethyl-N- (4
-Hydroxybutyl) amino] aniline (D-4) 2-methyl-N, N-diethyl-p-phenylenediamine (D-5) 2-methyl-4- [N-ethyl-N- (β
-Methanesulfonamidoethyl) amino] aniline (D-6) 2-methoxy-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (D-7) 4-methyl-3-methoxy-N, N-bis (3-hydroxypropyl) aniline (D-8) 4-amino-3-isopropoxy-N,
N-bis (β-hydroxyethyl) aniline (D-9) 1- (β-hydroxyethyl) -5-amino-6-methyl-indoline (D-10) 1,2,3,4-tetrahydro-1-
(3,4-dihydroxybutyl) -2,2,4,7-tetramethyl-6-amino-quinoline (D-11) 1,2,3,4-tetrahydro-1- (β
-Hydroxyethyl) -4-hydroxymethyl-6-amino-7-methyl-quinoline

In the color development processing B of the present invention, D-
1, D-2, D-3, D-6, D-7, D-8, D-1
0 and D-11 are particularly preferable, D-1, D-2 and D-3 are more preferable, and D-1 is the most preferable.

The concentration of the developing agent is 25 mmol or more and 80 mmol or less, preferably 25 mmol or more and 60 mmol or less, more preferably 27 mmol or more and 50 mmol or less, and particularly preferably 30 mmol or more and 45 mmol per liter of the processing liquid. It is below millimolar.

Within the concentration range of the developing agent, two or more developing agents may be used in combination.

In the color development processing B of the present invention, the bromide ion is particularly important as an antifoggant, and the Br ⁻ concentration is 15 mmol or more and 60 mmol or less, preferably 16 mmol or more and 42 mmol or less per liter of the processing liquid. And particularly preferably 16 mmol or more and 35 mmol or less.

Note that picolinic acid is added to the color developing solution of the development processing B as a compound that accelerates the release of the base from the poorly water-soluble basic metal compound, but the compound that accelerates is not limited to picolinic acid. Instead, it can be selected according to the type of basic metal compound.

The temperature of the treatment liquid is 40 ° C. or higher and 60 ° C. or lower, preferably 42 ° C. or higher and 55 ° C. or lower, and particularly preferably 43 ° C. or higher and 50 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 11.0 or less, preferably 10.0 or more and 10.5 or less.

Further, a silver halide solvent may be contained as a development accelerator, and thiosulfates, methanethiosulfonates, imidazoles described in JP-A-3-203735, and JP-A-4-130431 can be used. And the thioethers described in JP-A-4-317055 are preferred.

Color development processing A and / or B of the present invention
Can contain the following compounds. For example, other than hydroxylamine, diethylhydroxylamine,
Various hydroxylamines represented by the general formula (I) of JP-A-3-144446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids. Preservatives, organic solvents such as ethylene glycol, diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3-pyrazolidone, etc. Auxiliary developing agents, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid. , Shi B hexane diaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

Among the above, substituted hydroxylamine is most preferable as a preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable example is N, M-bis (2-sulfoethyl).
Hydroxylamine, monomethylhydroxylamine,
Diethyl hydroxylamine and the like can be mentioned.

Further, any antifoggant can be added.
As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Representative examples include nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

In order to maintain the pH of the color developing solution, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, use of a carbonate is preferred. The amount of the buffer added to the developer is preferably 0.1 mol / liter or more,
Particularly preferably, it is 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. Examples of this are JP-A-63-146998 and JP-A-63-199295.
JP-A-63-267750, JP-A-63-267
751, JP-A-2-229146, and JP-A-3-18.
6841, German Patent 3,739,610, European Patent 468,325 and the like can be cited as chelating agents. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferred as the liquid shielding agent. It is particularly preferable to use it as a replenisher. In addition, the replenishment amount is 1
30 to 800 ml, preferably 50 per square meter
It is about 500 ml. Any development accelerator can be added to the color developing solution of the present invention, if necessary. As a development accelerator, Japanese Examined Patent Publication Nos. 37-16088, 37-5987 and 38-7826
No. 44-12380, No. 45-9019 and U.S. Pat.
Thioether compounds represented by JP-A No. 247, etc.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, US Pat. No. 2,494,903,
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546, No. 2,596,92
6 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed.

Next, the desilvering process of the present invention will be described in detail. As the bleaching agent used in the processing solution having a bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate,
Bromate, hydrogen peroxide, and red blood salt are used,
The aminopolycarboxylic acid (III) complex can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) sulfate ammonium, etc.) may coexist to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in excess, it is usually preferably in the range of 0.01 to 10%.

In the present invention, the compounds forming a ferric complex salt in a liquid having a bleaching ability include ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the processing solution having bleaching ability of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, and 0.01 to 0.50 mol / liter.
The range of liter is preferable, and more preferably 0.02 to
It is in the range of 0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in a bath having a bleaching ability or a prebath thereof. For example, US Pat. No. 3,893,858,
German Patent No. 1,290,812, JP-A-53
-95630 and Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide bond, and JP-B-4.
5-8506, JP-A-52-20832, and 53-
Thiourea compounds described in US Pat. No. 32735, U.S. Pat. No. 3,706,561 and the like, or halides such as iodine and bromide ions are preferable because of their excellent bleaching power.

Other baths having a bleaching ability applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH buffering capacity of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid as required And at least one of inorganic acids, organic acids and alkali metal or ammonium salts thereof, or a corrosion inhibitor such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and the fixing agent component in the fixing solution are
Known fixing agents, ie, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a water-soluble silver halide dissolving agent such as a thioether compound such as octanediol, a mesoionic compound and thioureas, and these can be used alone or as a mixture of two or more. Also, Japanese Patent Application Laid-Open No. 55-15535
A special bleach-fixing solution comprising a combination of the fixing agent described in No. 4 with a large amount of a halide such as potassium iodide or the like can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate, is preferred. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 2 mol.
１．０1.0 mol. The bleach-fixing solution and the fixing solution of the present invention preferably contain sulfite (or bisulfite or metabisulfite) as a preservative, but especially 0.08 to 0.4 mol / liter, Preferably 0.
It is preferable to contain 1 to 0.3 mol / liter. By using this concentration range and further using the final bath of the present invention,
Not only the magnetic recording performance was remarkably improved, but also desirable results were obtained in terms of image storability. The bleach-fixing solution and the fixing solution of the present invention include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite) described above as preservatives. , Metabisulfite (eg, potassium metabisulfite, sodium metabisulfite,
In addition to containing sulfite ion-releasing compounds such as ammonium metabisulfite), aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.),
Ascorbic acids, hydroxylamines and the like can be added as necessary.

Further, a bleaching solution, a bleach-fixing solution and a fixing solution may be added with a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferred pH range is 4.5.
It is -6.2 and more preferably 5-6. Even if the pH is higher or lower than the present pH, the magnetic recording performance may not be sufficiently exhibited. In the case of a fixer, pH 5
About 8 is desirable.

Bleaching solution, bleach-fixing solution used in the present invention,
The replenishing amount of the fixing solution is 50 to 200 per 1 m ² of the light-sensitive material.
It is 0 ml, particularly preferably 100 to 1000 ml. Further, washing water as a post-bath or overflow solution of a stabilizing bath may be replenished as necessary. The processing temperature of the bleaching solution, the bleach-fixing solution and the fixing solution is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for aeration, and blowing of air into a processing solution having a bleaching ability or absorption of air using an ejector can be performed. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak's Z-121, Using Process C-41 No. 3
Edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
Page, upper right column, line 6-lower left column, line 2
Can be used as is.

In the desilvering step, it is preferable that stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and increasing the stirring effect by turbulently flowing the emulsion surface, and circulating the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The amount of washing water in the washing step depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the application, the washing water temperature, the number of washing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other factors. It can be set in a wide range depending on the condition.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picturean.
d Television Engineers Volume 64, P. 248-253 (1955)
May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 3 to 9, preferably 4 to 8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range is 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 are used.
Any of the known methods described in No. 1 can be used.

The stabilizing solution contains a compound for stabilizing a dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, an adduct of formaldehyde bisulfite, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids, pH buffers and the like are included. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. However, the lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole described in JP-A-4-270344, and N, N'-bis (1 4,3,4-triazol-1-ylmethyl) piperazine and the like.
Azolylmethylamines described in 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivative such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231105 is also preferable. .

The washing water and / or the stabilizing solution may contain various surface active agents in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

It is preferable to add various chelating agents to the wash water and / or the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N '.
-Trimethylene phosphonic acid, diethylene triamine-
Organic phosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid or EP 345,172A
The hydrolyzate of the maleic anhydride polymer described in No. 1 can be used.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water is calculated, the amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and water is supplied to the bleaching tank in proportion to the amount of evaporation.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
Tap water may be used as water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposited γFe ₂ O ₃
Co-coated ferromagnetic iron oxides such as The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like.
The specific surface area of _SBET is preferably 20 m ² / g or more, 30 m ² / g
The above is particularly preferred. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 161032. Further, magnetic particles having a surface coated with an inorganic or organic material described in JP-A-4-259911 and 5-81652 can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resin described in JP-A-4-219569, thermosetting resin,
Radiation curable resins, reactive resins, acids, alkali or biodegradable polymers, natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the above resin is -40 ℃ ~ 300 ℃, the weight average molecular weight is
It is 20,000 to 1 million. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based cross-linking agent, tolylene diisocyanate,
Isocyanates such as 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane). ), And polyisocyanates produced by condensation of these isocyanates, and are described in, for example, JP-A-6-59357.

As a method of dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight of the magnetic particles and the binder is preferably 0.5; 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g
/ m ² , more preferably 0.02 to 0.5 g / m ² . The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss,
Cast, spray, dip, bar, extrusion and the like can be used, and the coating solution described in JP-A-5-341436 is preferable.

For the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL starts from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448 and 63-89850, are described.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL is disposed adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid N.
o.307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Gl).
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition.
As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
Particularly, the thickness is preferably 0.05 to 0.6 μm. The grains may be regular grains or polydispersed emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains).
% Having a particle diameter within ± 40% of the average particle diameter).

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

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

As couplers in which the color forming dye has a suitable diffusibility, US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,
93 (pages 140-144); Latex for impregnation of oil-soluble organic compounds: Latex described in US Pat. (Especially I-, (1), (2), (6), (12)
(Columns 4-5), formulas in rows 5-10 of column 2 of US 4,923,787 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1,27 (pages 24-48); Anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), II-5-II of columns 25-38 of US 5,122,444
I-23, especially III-10, I-1 to III- on pages 8 to 12 of EP 471347A
4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48,
In particular, A-39, 42; a material that reduces the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15,
Especially I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; Hardener: JP-A 1-21
4845, page 17, H-1,4,6,8,14, US 4,618,573, columns 13-
Compounds (H-1 to 54) represented by formulas (VII) to (XII) of 23, compounds represented by the formula (6) at the lower right of page 8 of JP-A-2-214852 (H
-1 to 76), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: JP-A-62-168139
P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, in particular, 28, 29 of column 7;
US 4,923,790, columns 3-15, I-1 to III-43, especially II-
1,9,10,18, III-25; stabilizer, antifoggant: US 4,923,
793 columns 6-16 I-1 ~ (14), especially I-1,60, (2), (13),
Compounds 1-65, especially 3 in columns 25-32 of US 4,952,483
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1,12,18,27,35,36, b-5,27 to 2
V-1 to 23 on page 9, especially V-1, EP 445627A FI on pages 33 to 55
-1 to F-II-43, especially FI-11, F-II-8, 17 to 2 of EP 457153A
Page 8 III-1 to 36, especially III-1,3, WO 88/04794 8-26
A microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular compounds D-1 to 87 (compounds 1 and 519306A represented by formulas (1) to (3)). (Pages 3 to 28), US 4,2
Compounds 1 to 22 represented by the formula (I) of 68,622 (columns 3 to
10), compounds (1) to (4) of the formula (I) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention are
For example, page 28 of RD. No. 17643 mentioned above, 6 of the same RD.
From page 47, right column to page 648, left column, and No. 307105, page 879. Preferred are polyester-based supports. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is defined as 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as:
It is defined as the time until the film thickness reaches 1/2. The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is a photograph science and engineering of A. Green et al. (Photogr.Sci.Eng.), 19 square, 2, 124 to 129 can be measured by using a swellometer (swelling meter) of the type. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is
On the side opposite to the side with the emulsion layer, the total dry film thickness is 2 μm
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of 20 μm. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

Next, the polyester support used in the present invention will be described. For details, including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3). .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to
It is 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support, after surface treatment,
It may be carried out at any stage after application of the back layer (antistatic agent, slip agent, etc.) and after application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Examples include a copolymer using a monomer selected from acrylic acid, itaconic acid, maleic anhydride and the like as a starting material, polyethylene imine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
_{nO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
MoO ₃ , at least one selected from V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Fine particles of oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles of 0.8 μm or less in order to enhance the matting property. Particles (0.25μm), colloidal silica (0.03μm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present, and for miniaturization of the camera,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, the cartridge used in the present invention may be a cartridge that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
Different patrones may be used.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples as long as the gist of the present invention is not exceeded.

[0140]

【Example】

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.25 Silver iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-4 0.085 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.021 ExM-5 0.030 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.13 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0156]

[Table 2]

In Table 2, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

[0160]

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[0161]

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[0162]

[Chemical formula 26]

[0163]

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[0164]

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[0165]

[Chemical 29]

[0166]

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[0167]

[Chemical 31]

[0168]

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[0169]

[Chemical 33]

[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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Subsequently, as shown in Table 3 in the samples 102 and thereafter, the magenta couplers used in the seventh to ninth layers of the green-sensitive layer were changed in an equimolar amount or the basic metal compound of poor water solubility was used. The samples up to the sample 112 were prepared by adding or not adding. Regarding the polymer coupler among the magenta couplers, the constitutional unit of the polymer was converted to 1 mol and replaced. The poorly water-soluble basic metal compound was added as a fine particle dispersion having an average particle size of 0.3 μm.

These produced samples were cut and processed to have a width of 35 mm, and gradation exposure of white light was given, and one set was a conventional color development processing step and a development processing which was a processing solution. (I-1), the other set was subjected to accelerated color development processing step and development processing (II-1) which is a processing solution.

Process of (Development Process I-1) and Composition of Process Solution Process Time Process Temperature Color Development 3 min 15 sec 38 ° C. Bleach 1 min 00 sec 38 ° Bleach Fix 3 min 15 sec 38 ° C. Wash (1) 1 Minute 00 seconds 38 ℃ Washed with water (2) 1 minute 00 seconds 38 ℃ Dry 2 minutes 00 seconds 60 ℃

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N -Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water to 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05

(Bleaching Solution) Tank Solution and Replenishing Solution Common (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH _{3 ) 2 N-CH 2 -CH 2} -SS-CH 2 CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) was added to 15.0 ml water 1.0 l pH (adjusted with aqueous ammonia and nitric acid) 6.3

(Bleach-fixing solution) Tank solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / liter) 240.0 ml Ammonia water (27%) Add 6.0 ml water and 1.0 liter pH (adjust with ammonia water and acetic acid) 7.2

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-12 manufactured by Rohm and Haas).
0B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by dichloride. Sodium isocyanurate 20m
g / l and 150 mg / l sodium sulphate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-benzisothiazolin-3-one sodium 0.10 Ethylenediamine tetra Acetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1 liter pH 8.5

Process of (Development treatment II-1) and composition of treatment liquid Process temperature Time Color development 45 ° C. 60 seconds Bleach fixing 40 ° C. 60 seconds Water washing (1) 40 ° C. 15 seconds Water washing (2) 40 ° C. 15 seconds Water washing (3 ) 40 ℃ for 15 seconds Stability 40 ℃ for 15 seconds Drying 80 ℃ for 60 seconds (Washing was carried out in 3 tank countercurrent method from (3) to (1).)

Liquid composition (color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 4.0 Potassium iodide 1.3 mg Picolinic acid 12 Hydroxyl Amine Sulfate 1.5 Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline Sulfate 18.0 Water was added 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 (bleach-fixing solution) (unit mol) ethylenediamine- (2-carboxyphenyl) -N, N, N'-triacetic acid 0.17 ferric nitrate nonahydrate 0.15 Ammonium thiosulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Add water 1.0 Liter pH (prepared with acetic acid and ammonia) 5.8 (wash water) Same composition as described in (I-1) (Stabilizer) Same composition as described in (I-1).

The processed sample was subjected to density measurement for each of cyan, magenta and yellow, and its gradation was calculated from the obtained characteristic curve in accordance with the above-described method of calculating the gradation. Regarding the obtained gradations, the gradation degree γ of the development processing (I-1) for cyan, magenta, and yellow is set to γ _I
Then, the gradation γ of the development treatment (II-1) was defined as γ _II , and the ratio γ _II / γ _I was determined. Further, for the magenta color image, on the basis of no addition of the sparingly water-soluble basic metal compound to the comparative coupler, the γ ratio when added was based on the same addition to the coupler group of the present invention. And similar γ
Ratios were determined for Development Processes (I-1) and (II-1), respectively. Table 3 shows the results.

[0187]

[Table 3]

From the table, Samples 104 to 112 in which the coupler represented by the general formula (m) of the present invention was used in the green-sensitive layer and a poorly water-soluble basic metal compound was compared to Comparative Samples 101 to 103. On the other hand, as is clear from the gradation degree in the current development processing (I-1) and rapid processing (II-1),
It can be seen that the gradations of the magenta color image are almost the same, and the gradations of the three colors of cyan, magenta and yellow satisfy the conditional expression. From these results, it can be seen that it is possible to provide an image forming method that exhibits good magenta color development even when subjected to rapid processing, has excellent gradation balance of the three colors, and exhibits good tone reproducibility and color reproducibility.

Example 2 Using the samples 101 to 112 prepared in Example 1, the picolinic acid used in the color developer of the development treatment (II-1) was replaced with another trigger in an equimolar amount, and Similar evaluation was carried out. (Development processing II-2) The picolinic acid used in the color developing solution was replaced with 2,6-pyridinedicarboxylic acid in an equimolar amount. (Development processing II-3) Similarly, picolinic acid was replaced with 5-ethylpicolinic acid in an equimolar amount. (Development treatment II-4) Similarly, picolinic acid was replaced with oxalic acid in an equimolar amount.

The results are shown in Table 4. However, the ratio of γ _II-2 to γ _II-4 and γ _I-1 for cyan and yellow is shown in Example 1.
Since it was the same as, it was omitted.

[0191]

[Table 4]

From the table, the gradation of the magenta color image obtained from the developing treatments (II-1) to (II-4) is almost the same as that of the developing treatment (I-1), as in the case of Example 1. It can be seen that the conditional expression of gradation is satisfied. As a result, an image showing good magenta color development even after rapid processing, an excellent gradation balance of three colors of cyan, magenta, and yellow, and good tone reproducibility and color reproducibility regardless of which processing is performed. It is understood that a forming method can be provided.

Example 3 Using the samples 101 to 112 produced in Example 1, gradation exposure of white light was applied in the same manner as in Example 1, and continuous (running) processing and development processing (A-1) shown below were carried out. And development processing (B-1) were carried out. In addition, as for continuous processing, both samples were processed using the sample 101, and the images taken by the camera were processed by 1 m ² every day every day until the replenisher of 3 times the tank capacity of the color developing solution was consumed, and then the development processing was performed. went.

The treated sample was evaluated in the same manner as in Example 1. The result is the same as the result shown in Table 3 of Example 1, and the gradation of the magenta color image obtained even when the rapid continuous processing is performed is almost the same as that of the development processing II-1. And the gradation balance of the three colors of cyan, magenta and yellow was good. Therefore, it is understood that the image forming method is excellent in tone reproducibility and color reproducibility even when the same light-sensitive material is passed through both treatments.

As in Example 2, the same results as in Example 2 can be obtained even when continuous processing is carried out using the trigger used for the color developing solution in the rapid development processing.

(Development processing A-1) processing step and liquid composition (processing step) step processing time processing temperature replenishment amount ^* tank capacity color development 3 minutes 5 seconds 38.0 ° C. 23 ml 17 liters bleaching 50 seconds 38.0 ° C. 5 ml 5 liters Bleaching fixing 50 seconds 38.0 ° C-5 liters fixing 50 seconds 38.0 ° C 16 ml 5 liters Water washing 30 seconds 38.0 ° C 34 ml 3.5 liters Stability (1) 20 seconds 38.0 ° C-3 liters Stability (2) 20 seconds 38.0 ° C 20 ml 3 liter Dry 1 min 30 sec 60 ° C * Replenishment amount per 35 mm width of photosensitive material 1.1 m (equivalent to 24Ex.) Stabilizer is countercurrent method from (2) to (1), The overflow of washing water was introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. I was allowed to flow in. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the bleach-fixing step, the amount of the bleach-fixing liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm width of the photosensitive material. 2.5 ml, 2.0 ml, 1 m, respectively.
0 ml and 2.0 ml. Also,
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 disodium-N, N-bis (sulfonate ethyl) hydroxylamine 1.5 2.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.8 6.5 1.0 liter by adding water 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Monohydrate 130 195 Ammonium Bromide 70 105 Ammonium Nitrate 14 21 Hydroxyacetic Acid 50 75 Acetic Acid 40 60 Water 1.0 liter 1.0 liter pH [prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixing solution) Tank solution (g) Replenishing solution (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing water) Common for tank liquid and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strongly basic anion exchange resin (Amberlite IR). -400) was passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg / liter of sodium diisocyanurate dichloride and 150 mg / liter of sodium sulfate were added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 1,2-Benzisothiazoline-3- On sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 (Development treatment Step B-1) and composition of processing solution (processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 60 seconds 45.0 ℃ 260 ml 1 liter Bleach 20 seconds 45.0 ℃ 130 ml 1 liter Fixed 40 seconds 45.0 ℃ 100 ml 1 liter water wash (1) 15 seconds 45.0 ° C-1 liter water wash (2) 15 seconds 45.0 ° C-1 liter water wash ( 3) 15 seconds 45.0 ° C 400 ml 1 liter Dry 45 seconds 80 ° C * Replenishment amount per 1 m ² of light-sensitive material (4 steps counter-current multi-stage cascade for washing from (3) to fixing)

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.0-Potassium iodide 1.3 mg-picolinic acid 12 14.4 disodium-N, N-bis (sulfonate ethyl) hydroxylamine 12.0 17.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.5 15.0 Water In addition 1.0 liter 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (mol) Replenishing solution (mol) 1,3-diaminopropanetetraacetic acid ferric salt ammonium monohydrate 0.33 0.50 ferric nitrate nonahydrate 0.30 4.5 ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.5 4.0

(Fixer) Common to tank and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml imidazole 15 Ethylenediaminetetraacetic acid 15 Water-added 1.0 liter pH (prepared with ammonia water and acetic acid) 5.8

(Washing Water) The same composition as the washing water of (Development Treatment A-1) was used.

(Stabilizing Solution) The same composition as the stabilizing solution used in (Development Processing A-1) was used.

Example 4 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, 300
After melting at ℃, extruded from T-die, longitudinally stretched 3.3 times at 140 ℃, then transversely stretched 3.3 times at 130 ℃, further heat set at 250 ℃ for 6 seconds and 90 μm thick. PEN
I got a film. This PEN film contains blue dye, magenta dye and yellow dye (I-1, I-4, I-6, I-24, I-26, I- described in Public Technical Report No. 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both surfaces thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were formed on each surface. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02g / m ² , poly (degree of polymerization 10)
Coated with 0.005 g / m ^{2 of} oxyethylene-p-nonylphenol and resorcin. 3-2) Coating of magnetic recording layer 3-Poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89enu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² is diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed by an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0 as a curing agent .
The 3 g / m ^2, acetone as a solvent, methyl ethyl ketone,
Coating was performed with a bar coater using cyclohexanone and dibutyl phthalate to obtain a magnetic recording layer having a thickness of 1.2 μm. C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ 50 mg / m ² as a slip agent, silica particles (0.3 μm) as a matting agent and 3-poly (degree of polymerization 1
5) Abrasive aluminum oxide treated and coated with oxyethylene-propyloxytrimethoxysilane (15% by weight)
(0.20 μm and 1.0 μm) at 50 mg / m ² and
It was added to 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes (all the rollers and conveyors in the drying zone are 115
° C). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, the coercive force is 7.3 × 10 ⁴ A / m, and the squareness ratio is Was 65%.

3-3) Preparation of Sliding Layer A mixture of C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (6 mg / m ² ) was applied. This mixture was prepared by melting in xylene / propylene monomethyl ether (1/1) at 105 ° C and pouring and dispersing in propylene monomethyl ether (10 times volume) at room temperature. (Average particle size 0.01 μm)
And then added. Drying was performed at 115 ° C for 6 minutes (115 ° C for all rollers and conveying devices in the drying zone). The sliding layer has a dynamic friction coefficient of 0.10 (5 mmφ stellen hard spheres, a load of 100
g, speed 6 cm / min), coefficient of static friction 0.08 (clip method), and coefficient of dynamic friction between the emulsion surface and the sliding layer described later is 0.13.
And excellent characteristics.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, multi-layer coating of each layer having the same composition as in Example 1 was carried out to prepare a color negative film. These are designated as Samples 401 to 412.

The light-sensitive material prepared as described above has a width of 24 mm,
Cut it to 160 cm, and add a 2 mm square perforation 0.7 mm from the width of one side of the photosensitive material.
Two are provided at 5.8 mm intervals. These two sets are provided at intervals of 32 mm and are made into FIG. 1 to FIG. 7 of US 5,296,887.
In a plastic film cartridge described in (1). An FM signal was recorded on this sample at a feed rate of 1.000 / s during the above-mentioned perforation of the photosensitive material using a head capable of inputting and outputting with a head gap of 5 μm and a number of turns of 2,000 from the coated surface side of the magnetic recording layer.

For these light-sensitive materials, both continuous processing and development processing A- used in Example 3 were carried out in the same manner as in Example 1.
1 and development processing B-1 were carried out to evaluate the performance. The result is the same as the result obtained in Example 3 and the same as the result shown in Table 3 of Example 1, and the light-sensitive material 1 of the present invention is the same.
Nos. 04 to 112 showed good magenta color development, the ratio of gradations obtained from both processes satisfied the conditional expression, and it was clear that the gradation balance of three colors of cyan, magenta and yellow was excellent.

Further, with respect to the above-mentioned light-sensitive materials, Zoom Cardia (manufactured by Fuji Photo Film Co., Ltd.) was modified so that the cartridge could be loaded, and a Macbeth chart was photographed using each light-sensitive material, and both developments were performed. Fuji Color Paper F is processed using these color negatives.
The image quality was visually evaluated by printing on A (V). As a result, the color print using the color negative obtained from both processings of the light-sensitive materials 404 to 412 of the present invention had good tone reproduction and color reproducibility in the gray portion. On the other hand, in Comparative Photosensitive Materials 401 to 403, the gradation balance of the three colors was poor in both processes, and the tone reproducibility and color reproducibility of the gray portion were remarkably poor.

[0216]

According to the present invention, the specific magenta coupler represented by the general formula (m) is incorporated in the green-sensitive silver halide emulsion layer of the light-sensitive material, and at least one of the light-sensitive layer and the non-light-sensitive layer is water-resistant. Even if these photosensitive materials using soluble basic metal compounds are subjected to two types of color development processing with different color development times, that is, the current development processing and rapid development processing, the magenta color obtained from both processings is good. Therefore, even if a conditional expression that defines the gradient obtained from both processes is set,
Provided is an image forming method of a silver halide color photographic light-sensitive material excellent in tone reproducibility and color reproducibility by satisfying the conditional expression and having a good gradation balance of three colors of cyan, magenta and yellow. it can.

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[Procedure amendment]

[Submission date] September 11, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

[0058]

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─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 7/00 530 G03C 7/00 530 550 550 7/20 7/20 7/26 7/26 7 / 392 7/392 Z 7/407 7/407

Claims (4)

[Claims] 1. A red-sensitive silver halide emulsion layer on a support,
A silver halide color photographic light-sensitive material having at least one green-sensitive silver halide emulsion layer, at least one blue-sensitive silver halide emulsion layer, and at least one non-light-sensitive layer, and a general formula for the green-sensitive silver halide emulsion layer of the photographic light-sensitive material. A silver halide color photographic light-sensitive material containing the coupler represented by (m) and containing at least one layer of a poorly water-soluble basic metal compound is subjected to the following two types of development treatments with different color development times ( When I) and development processing (II) are carried out, the
A silver halide color photographic light-sensitive material characterized in that the gradations of cyan, magenta and yellow obtained by various types of development processing satisfy the following conditional expressions. General formula (m) (In the formula, R ₁ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group, and Ar is a phenyl group or 1
Represents a phenyl group substituted with at least one halogen atom, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, a sulfonyl group or a sulfamoyl group, and X is an aromatic primary amine developing agent. Represents a group capable of splitting off by a coupling reaction with the oxidant of the above, which is bonded to the 4-position of the pyrazolone skeleton with a sulfur atom. ) Conditional expression 0.8 ≦ γ _II (Y) / γ _I (Y) ≦ 1.2 0.8 ≦ γ _II (M) / γ _I (M) ≦ 1.2 0.8 ≦ γ _II (C) / Γ _I (C) ≦ 1.2 (γ _I (Y), γ _I (M), γ _I (C) respectively represent the gradation levels of yellow, magenta, and cyan when the development processing I is carried out, and γ _II (Y), γ _II (M), γ _II (C)
Represents the gradation levels of yellow, magenta, and cyan when the development processing II was carried out. (Development Treatment I) Color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N-as a color developing agent. (Β-
A development process characterized in that the color development process is performed using a color development solution containing 15 to 20 mmol / L of hydroxyethyl) amino] aniline. (Development Treatment II) Color development time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N- (β-hydroxy) is used as a color developing agent. 35-40 mmol of ethyl) amino] aniline /
A developing treatment, characterized in that the color developing treatment is carried out using a color developing solution containing a compound which promotes the release of a base from a basic metal compound having a solubility in water and a poorly water-soluble basic metal compound. 2. The halogenated product according to claim 1, wherein the photographic light-sensitive material has a magnetic layer containing a ferromagnetic powder in a back layer on the side opposite to the side of the photosensitive emulsion layer with the support interposed therebetween. Silver color photographic light-sensitive material. 3. A color image forming method, which comprises forming a color image by carrying out the development processing A described below, using the silver halide color photographic light-sensitive material according to claim 1 or 2. (Development treatment A) The color developing time is 150 to 200 seconds, the temperature of the color developing solution is 37 to 40 ° C., and a color developing solution containing 15 to 20 mmol / liter of a color developing agent is used. Development process. 4. A color image forming method, wherein a color image is formed by carrying out the following development processing B using the silver halide color photographic light-sensitive material according to claim 1 or 2. (Development treatment B) Color development time is 25 to 90 seconds, temperature of color developing solution is 40 to 60 ° C., concentration of color developing agent is 25 to 80 mmol / liter, and basic metal compound hardly soluble in water is used. A development process comprising using a color developing solution containing a compound that accelerates the release of a base.