JPH08190182A - Color image forming method - Google Patents

Abstract

PURPOSE: To obtain a color image forming method capable of shortening a color development time and enhancing color reproduction performance and image preservability by color developing a specified silver halide color photographic sensitive material in the presence of a color developing agent of a tetrahydroquinoline derivative. CONSTITUTION: The silver halide color photographic sensitive material contains at least one kind of yellow coupler having a pKa of 6.2-11.0 in an active coupling site and represented by formula I in at least one hydrophilic colloidal layer formed on a support, and it is color developed in the presence of at least one kind of developing agent of the tetrahydroquinoline derivative represented by formula II. In formulae I and II, Ra is an alkyl or cycloalkyl group or the like; Rb is a halogen atom or an alkoxy group or the like; Rc is a group substitutable on the benzene ring; X is a group to be released by coupling reaction with the oxidation product of a developing agent; each of (m) and (n) is an integer of 0-3; each of R1 -R6 is an H atom or a substituent; and each of R7 and R8 is a substituent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method, and more particularly to a color image forming method which can shorten processing time and improve color reproducibility and image storability.

[0002]

2. Description of the Related Art In recent years, due to an increase in in-store processing called minilabs and an increase in the amount of color negative film used in the field of news photography, development processing can be completed in a shorter time, and prints can be immediately provided to customers or newspapers. There is a rapid increase in the demand for publication in the etc. In particular, regarding the processing of a color negative film, which requires a longer time than that of a color paper, there is a particularly high demand for shortening the processing time. Regarding shortening of the color developing step among the processing steps, JP-A-4-45440 discloses a method using a tetrahydroquinoline or a dihydroindole derivative as a color developing agent. It is described in the patent that even in a color photographic light-sensitive material mainly composed of a silver iodobromide emulsion such as a color negative film, it is possible to shorten the color development step by using these compounds as a color developing agent. ing.

However, when an attempt is made to shorten the color developing process by using a color developing agent as described in the patent, the development of a layer (lower layer) near the support is controlled by the supply rate of the developing agent. The development is delayed compared to the development of a layer (upper layer) far from the body, and as a result, the color balance is largely lost and the color reproducibility is significantly deteriorated. Further, when stored in a room after processing for a long period of time, the density of the minimum color image density portion (Dmin) of the light-sensitive material is greatly increased (hereinafter referred to as color development over time), which causes a problem in image storability.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color image forming method which shortens the color development time and is excellent in color reproducibility and image storability.

[0005]

The above-mentioned objects have been achieved by the following color image forming method. That is, a yellow coupler represented by the following general formula (I) in at least one hydrophilic colloid layer provided on a support and having a pKa at the coupling active site of 6.2 or more and 11.0 or less. A color image forming method, which comprises color-developing a silver halide color photographic light-sensitive material containing at least one of the following in the presence of at least one tetrahydroquinoline-based color developing agent represented by the following general formula (D). Achieved by General formula (I)

[0006]

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[In the above formula (I), R _a represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an aryloxy group or a di-substituted amino group, and R _b represents a halogen atom or an alkoxy group. Represents a group, a cycloalkoxy group, an aryloxy group, an alkyl group, or a dialkylamino group, R _c represents a group substitutable on the benzene ring, and X is removable by a coupling reaction with an oxidized product of a developing agent. Represents a group, and n represents an integer of 0 to 3. General formula (D)

[0008]

[Chemical 4]

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R
₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each combination of R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ , at least one set is a substituent. R ₇ and R ₈ represent a substituent. m represents an integer of 0 to 3. In the color image forming method, the color developing time is 25 seconds or more and 90 seconds or more.
Seconds or less are preferable, and more preferably 30 seconds or more and 60 seconds or less.

The pKa of the yellow coupler of the present invention is determined by the following method. Tetrahydrofuran / water 6: 4 with 0.01 mmol coupler dissolved
To 100 ml of (weight ratio) solution 1N sodium chloride.
Add 5 ml and stir in a nitrogen gas atmosphere while stirring to 0.5
Titrate with an aqueous potassium hydroxide solution of N 2. The pH at the center of the inflection point of the titration curve with the horizontal axis as the dropping amount of the aqueous potassium hydroxide solution and the vertical axis as the pH value was defined as pKa. When there are multiple inflection points, that is, in the case of a coupler having a dissociation site in addition to the coupling active position (keto body or enol body), the UV absorption spectrum is monitored at the same time and the coupler around 260 to 350 nm is detected. The inflection point can be determined by examining the change in absorption of anions (dissociated products at the coupling active position).

The pKa of the coupler of the present invention is 6.2 or more 1
It is 1.0 or less, preferably 6.5 or more, and more preferably 7.0 or more.

The formula (I) will be described in detail below. In formula (I), R _a may be either substituted, alkyl group having carbon atoms 1 to 36 (preferably 4 to 24), -C 3-36 (preferably 4-2
4) cycloalkyl group, C6-C36 (preferably 6-24) aryl group, C1-C36 (preferably 1-24) alkoxy group, C3-C3
6 (preferably 3 to 24) cycloalkoxy group, C 6 to 36 (preferably 6 to 24) aryloxy group, or 2 to 36 carbon atoms (preferably 2 to 2)
It represents the di-substituted amino group of 4). Examples of substituents for these groups include halogen atoms (F, Cl, Br, I and so on), cyano groups, nitro groups, alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, aryloxy groups,
Acyloxy group, carbonamido group, sulfonamide group, alkoxycarbonylamino group, ureido group, carbamoyl group, sulfamoyl group, acylsulfamoyl group, acylcarbamoyl group, hydroxyl group, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group There are groups, amino groups, imido groups, alkylthio groups, arylthio groups, heterocyclic groups or acyl groups.

In the formula (I), R _b is a halogen atom,
Alkoxy group having 1 to 36 carbon atoms (preferably 1 to 24), cycloalkoxy group having 3 to 36 carbon atoms (preferably 3 to 24), and 6 to 36 carbon atoms (preferably 6).
To 24) aryloxy group, C1 to C16 (preferably C1 to C4) alkyl group or C2 to C2
It represents 4 (preferably 2 to 16) dialkylamino groups. Examples of substituents for these groups include halogen atoms, alkyl groups, alkoxy groups, aryloxy groups or alkoxycarbonyl groups.

In the formula (I), R _c represents a group which can be substituted on the benzene ring, and is preferably a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group or an aryloxy. Base,
Alkylthio group, arylthio group, acyl group, acyloxy group, carbonamido group, sulfonamide group, alkoxycarbonylamino group, ureido group, sulfamoylamino group, carbamoyl group, sulfamoyl group, acylcarbamoyl group, acylsulfamoyl group, It represents an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group or an imide group.

In the formula (I), n represents an integer of 0 to 3, and when n is plural, plural R _c may be the same or different. At least one of R _c has 6 carbon atoms.
To 36 (preferably 8 to 24).

In the formula (I), X is a halogen atom, an acyloxy group having 1 to 36 carbon atoms (preferably 2 to 24 carbon atoms), an aryloxy group having 6 to 36 carbon atoms (preferably 6 to 24 carbon atoms), and a carbon atom. Number 6 to 36 (preferably 6 to 2)
4) represents an arylthio group or a heterocyclic group having 2 to 36 carbon atoms (preferably 2 to 24). These groups may be substituted with the substituents mentioned in the description of _Ra above.

The preferred partial structure of the yellow coupler of the present invention represented by formula (I) will be described below. R _a is preferably _a tertiary alkyl group or a cycloalkyl group (including a polycyclic cycloalkyl group), an alkoxy group, a cycloalkoxy group or a di-substituted amino group. R _b is preferably F, Cl, a trifluoromethyl group, an isopropyl group, a t-butyl group, a methoxy group, a cyclohexyloxy group, a phenoxy group, a 4-methoxyphenoxy group or a pyrrolidino group. R _c is preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. n is preferably an integer of 1 or 2. X is preferably an aryloxy group, an azolyl group (pyrrolyl, imidazolyl, pyrazolyl, triazozolyl, tetrazolyl) or a 5- to 6-membered heterocyclic group having one or more carbonyl groups bonded to the 1-position nitrogen atom (for example, imidazolidine-2. , 4-dione-3
-Yl, 1,2,4-triazolidine-3,5-dione-4-yl, oxazolidin-2,4-dione-3-yl, thiazolidin-2,4-dione-3-yl, imidazolidine-2, 4,5-trione-1-yl, 2-imidazolone-1-yl, 5-tetrazolone-1-yl, 2
-Pyridone, 4-pyridone, xanthin-9-yl).

In the formula (I) below, R _a , R _c and X
A specific example of R _a example

[0019]

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[0020]

[Chemical 6]

Examples of R _c

[0022]

[Chemical 7]

[0023]

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Example of X

[0025]

[Chemical 9]

[0026]

[Chemical 10]

Specific examples of the yellow coupler represented by the formula (I) are shown below, but the invention is not limited thereto. Numerical values in parentheses represent pKa values.

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

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[0032]

[Chemical 15]

[0033]

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The yellow couplers of the present invention represented by the formula (I) are disclosed in JP-A-47-26133 and 51-1026.
No. 36, No. 55-598, No. 55-161239,
63-43144, JP-A-4-174428, 4-184434, 4-190346 and 4-2.
18042, 5-111416, 5-80469
U.S. Pat. Nos. 3,408,194 and 3,933.
501, Research Disclosure 1805
No. 3 (1979) and the like. The yellow coupler of the present invention can be added to any layer of the light-sensitive material, but is preferably added to a blue-sensitive silver halide emulsion layer or an adjacent layer, more preferably to a blue-sensitive silver halide emulsion layer. Is the addition of. The amount of the yellow coupler of the present invention added to the light-sensitive material is 0.1 to 5 g / m ² , preferably 0.2 to ² g / m ² , and more preferably 0.3 to 1.5 g / m ² .

In the present invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ in the compound represented by the general formula (D),
R ₇ , R ₈ and m will be described in detail below. R ₁ , R
₂ , R ₃ , R ₄ , R ₅ , and R _{6, which} may be the same or different, each represents a hydrogen atom or a substituent. More specifically, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are hydrogen atoms or substituents, and examples of the substituents include halogen atoms, alkyl groups, aryl groups, heterocyclic groups, and cyano groups. , Nitro group, hydroxyl group, carboxyl group, sulfo group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonyl Amino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, Heterocyclic thio group, sulfinyl group, phosphonyl group, ari Le oxycarbonyl group, an acyl group. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good.

More specifically, R ₁ , R ₂ , R ₃ , R ₄ ,
Examples of the substituents of R ₅ and R ₆ are shown below. The halogen atom is, for example, a fluorine atom or a chlorine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3 -Hydroxypropyl, benzyl, 2
-Methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3- Dihydroxypropyl, 3,4-dihydroxybutyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl,
2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl1-methylethyl,
It is 4-nitrobutyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocyclic ring containing 1 or more oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The number of the elements may be one or more, and examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl and pyrazolyl. The alkoxy group is an alkoxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m- (3
-Hydroxypropionamido) phenoxy. The acylamino group is an acylamino group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, for example, acetamide, 2
-Methoxypropionamide, p-nitrobenzoylamide. Alkylamino group has 1 to 1 carbon atoms
6, preferably an alkylamino group having 1 to 6 carbon atoms, such as dimethylamino, diethylamino and 2-hydroxyethylamino. Anilino group has 6 to 2 carbon atoms
Anilino group 4 is, for example, anilino, m-nitroanilino, N-methylanilino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
-16, preferably a sulfamoylamino group having 0 to 6 carbon atoms, such as dimethylsulfamoylamino, methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkylthio group has 1 to 1 carbon atoms.
16, preferably an alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 24 carbon atoms, and examples thereof include phenylthio, 2-carboxyphenylthio, and 4-cyanophenylthio. The alkoxycarbonylamino group has 2 to 2 carbon atoms.
16, preferably an alkoxycarbonylamino group having 2 to 6 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropoxycarbonylamino. The sulfonamide group is a sulfonamide group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfonamide, p-toluenesulfonamide, and 2-methoxyethanesulfonamide. The carbamoyl group is a carbamoyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include carbamoyl, N, N-dimethylcarbamoyl and N-ethylcarbamoyl. The sulfamoyl group has 0 to 1 carbon atoms
6, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl. C1 as a sulfonyl group
To 16, preferably an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, and examples thereof include methanesulfonyl, ethanesulfonyl, and 2-chloroethanesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl. The heterocyclic oxy group has 1 to 1 carbon atoms.
5 is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one oxygen atom, nitrogen atom, or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element are 1 However, it may be plural, for example, 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, and 2-pyridyloxy.

The azo group is an azo group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as phenylazo or 2-
Hydroxy-4-propanoylphenylazo and 4-sulfophenylazo. The acyloxy group is an acyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group is a carbamoyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxy. The silyl group is a silyl group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyl, isopropyldiethylsilyl,
It is t-butyldimethylsilyl. The silyloxy group is a silyloxy group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, and examples thereof include trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonylamino, 4-cyanophenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The imide group has 4 to 1 carbon atoms
The imide group of 6 is, for example, N-succinimide or N-phthalimide. Heterocyclic thio group has 1 to 5 carbon atoms
Is a 5- or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element may be one There may be a plurality, for example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfinyl group has 1 to 16 carbon atoms,
Preferred is a sulfinyl group having 1 to 6 carbon atoms, and examples thereof include methanesulfinyl, benzenesulfinyl, and ethanesulfinyl. The phosphonyl group has 2 to 1 carbon atoms
6, preferably a phosphonyl group having 2 to 6 carbon atoms, for example,
Methoxyphosphonyl, ethoxyphosphonyl and phenoxyphosphonyl. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonyl, 2-methylphenoxycarbonyl and 4-acetamidophenoxycarbonyl. The acyl group is an acyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetyl, benzoyl,
It is 4-chlorobenzoyl.

As R ₅ and R ₆ , an alkyl group, an aryl group or a heterocyclic group is preferable. However, when R ₅ and R ₆ are heterocyclic groups, they are bonded to carbon atoms constituting the heterocycle of the heterocyclic group. R ₇ and R ₈ are substituents, and in this case, the substituents include the substituents described in R _{1 to} R ₆ . It preferably represents an alkyl group, an aryl group or a heterocyclic group. However, when R ₇ is a heterocyclic group, the nitrogen atom in the general formula (D) to which R ₇ is bonded is linked to the carbon atom forming the heterocycle of the heterocyclic group. m represents an integer of 0 to 3.

Among the compounds represented by the general formula (D),
The compound represented by the following general formula (DD) is particularly preferable. General formula (DD)

[0043]

[Chemical 17]

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R
₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each combination of R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ , at least one of them is a substituent. R ₇ represents a substituent.
R ₉ represents a hydrogen atom or a substituent.

R ₁ , R ₂ , R ₃ , R in the general formula (DD)
Preferred combinations of ₄ , R ₅ , R ₆ , R ₇ and R ₉ will be described below. R ₉ is a hydrogen atom, an alkyl group or an alkoxy group, R ₇ is an alkyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Is preferably a hydrogen atom or an alkyl group. Here, the alkyl group and the alkoxy group include those substituted with other substituents. In this combination,
More preferably, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ is an alkyl group substituted with a water-soluble group, and further a hydroxyl group or a carboxyl group. It is preferably an alkyl group substituted with a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or a sulfonyl group. Particularly, an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group or a sulfonamide group is preferable.

As a more preferable combination, R ₉ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
To R 6 are alkoxy groups, R ₇ is an alkyl group having 1 to 6 carbon atoms, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R _{6 are}
Is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this combination, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ is more preferably an alkyl group substituted with a water-soluble group, and further a hydroxyl group , An alkyl group substituted with a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or a sulfonyl group. Of these, an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group is particularly preferable.

As a more preferable combination, R ₉ is an alkyl group having 1 to 6 carbon atoms, and R ₇ is 1 to 6 carbon atoms.
And R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this combination R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉
It is more preferable that at least one of them is an alkyl group substituted with a water-soluble group, and further, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, or sulfamoyl. An alkyl group substituted with an amino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or a sulfonyl group is preferable, and an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group is particularly preferable. Is preferred.

As a more preferred combination, R ₉ is a methyl group, R ₇ is an alkyl group having 1 to 6 carbon atoms, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each A combination of a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In this combination, R ₁ , R ₂ , R
It is more preferable that at least one of ₃ , R ₄ , R ₅ , R ₆ and R ₇ is an alkyl group substituted with a water-soluble group, and further, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, Amino group, alkylamino group, ureido group, sulfamoylamino group, sulfonamide group, carbamoyl group, sulfamoyl group,
Alternatively, an alkyl group substituted with a sulfonyl group is preferable, and an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group is particularly preferable. Next, the general formula (D) in the present invention
Specific examples of the representative developing agent represented by are shown below, but the developing agent is not limited thereto.

[0049]

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[0050]

[Chemical 19]

[0051]

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[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

Since the compound represented by the general formula (D) is extremely unstable when stored as a free amine,
In general, it is preferable to produce and store a salt of an inorganic acid or an organic acid so that a free amine is not formed until the salt is added to the treatment liquid. Examples of the inorganic or organic acid for forming the salt of the compound of the general formula (D) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, naphthalene-
1,5-disulfonic acid and the like can be mentioned. Of these, salts of sulfuric acid and p-toluenesulfonic acid are preferable, and salts of sulfuric acid are most preferable. The color developing agent of the present invention is, for example, Journal of the
It can be easily synthesized according to the method described in American Chemical Society, Vol. 73, page 3100 (1951). Further, the following synthesis examples and methods similar thereto can also be used. Synthesis example 1. According to the following formula, the exemplary compound of the present invention (D-3
0) was synthesized.

[0059]

[Chemical 27]

Synthesis of (1-a) According to the method described in Organic Syntheses Collective Volume III, page 328, 214 g of m-toluidine (1-a)
78.0 g was obtained. Synthesis of (1-b) 250 ml of ethanol was added to 69.6 g of (1-a) and dissolved, 0.55 g of 10% palladium carbon was added, and the mixture was contacted with hydrogen for 5 hours in an autoclave. Then, the catalyst was filtered off using Celite as a filter aid, and the filtrate was concentrated (1
-B) 69.1 g was obtained. Synthesis of (1-c) To 498 ml of 3-chloro-1,2-propanediol, 680 ml of acetone and 2.2 g of p-toluenesulfonic acid monohydrate were added, and the mixture was left at room temperature for 15 hours. afterwards,
Concentrated, ethyl acetate was added to the residue, washed with water in which 2.0 g of sodium hydrogen carbonate was dissolved, washed with saturated saline, dried over sodium sulfate, and concentrated to obtain 244 g of (1-c). Synthesis of (1-d) To 73.5 g of (1-b), 150 ml of N, N-dimethylacetamide, 292 g of (1-c), 34.2 g of sodium hydrogencarbonate, 61.1 g of sodium iodide were added, and 150
Stirring was continued for 24 hours at 0 ° C. This was poured into water, extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated. To this, 388 ml of water and 71 ml of 12N hydrochloric acid were added, and after stirring at room temperature for 5 hours, 84 g of sodium hydrogen carbonate
Was added, extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate and concentrated, and purified by silica gel column chromatography to obtain (1-d) 43 g. Synthesis of (1-e) Methanol 31 was added to 2,5-dichloroaniline 30.8 g.
0 ml and 95 ml of 12N hydrochloric acid were added, and an aqueous solution prepared by dissolving 13.1 g of sodium nitrite in water was added dropwise while stirring with ice cooling. During the dropping, stirring was hindered by the precipitate, so the mixture was diluted with an appropriate amount of methanol. This is (1-d)
41.7 g of methanol to 420 ml of sodium acetate 1
To the suspension containing 04 g was added while stirring with ice cooling. afterwards,
This was poured into water and the precipitated crystals were collected by filtration, dissolved in ethyl acetate, washed with saturated brine, dried over sodium sulfate and concentrated, and purified by silica gel column chromatography.
e) 56.2 g were obtained. Synthesis of Exemplified Compound (D-30) (1-e) 55.8 g and 10% Palladium on carbon 0.5 g
Was added to 200 ml of methanol and contacted with hydrogen for 2 hours in an autoclave. Next, the catalyst was filtered off using Celite as a filter aid, and the filtrate was added dropwise to a methanol solution of 36.8 g of 1,5-naphthalenedisulfonic acid tetrahydrate. The precipitated crystals were collected by filtration, and the desired exemplary compound (D-
30.2 g of 1,5-naphthalenedisulfonate of 30) was obtained as colorless crystals. Melting point 245 ° C-251 ° C (decomposition).

Synthesis Example 2. The exemplified compound (D-18) of the present invention was synthesized according to the following formula.

[0062]

[Chemical 28]

Synthesis of (2-d) 150 ml of N, N-dimethylacetamide was added to 56.8 g of (1-b), 98.8 g of (2-c) sodium hydrogen carbonate 7
Add 6.0 g and 45.0 g of sodium iodide, and add 130
Stirring was continued for 12 hours at 0 ° C. This was poured into water, extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated. The obtained residue was purified by silica gel column chromatography to obtain (2-d) 88.8 g. Synthesis of (2-e) 450 ml of methanol was added to 88.8 g of (2-d) to dissolve it, and 79.3 ml of concentrated hydrochloric acid was added dropwise thereto over 10 minutes under ice cooling. After stirring for 5 hours, an aqueous solution prepared by dissolving 21.3 g of sodium nitrite in 40 ml of water was added dropwise over 15 minutes, and then stirred for 1 hour. After adding 1 liter of ethyl acetate and 1 liter of water thereto, 90 g of sodium hydrogen carbonate was added and stirred, and then an extraction operation was performed. The obtained ethyl acetate layer was washed with saturated brine, dried over sodium sulfate, and concentrated. The obtained residue was purified by silica gel column chromatography to obtain (2-e) 55.3 g. Synthesis of Exemplified Compound (D-18) (2-e) 55.3 g and 10% Palladium on carbon 1.0 g
Was added to 200 ml of methanol and contacted with hydrogen in an autoclave for 2 hours. Next, the catalyst was filtered off using Celite as a filter aid, and the filtrate was added dropwise to a methanol solution of 64.8 g of 1,5-naphthalenedisulfonic acid tetrahydrate. The precipitated crystals were collected by filtration, and the desired exemplary compound (D-
188.0 g of 1,5-naphthalenedisulfonate of 18) was obtained as colorless crystals. Melting point 264-267 ° C (decomposition)

Synthesis Example 3. The exemplary compound (D-32) of the present invention was synthesized according to the following formula.

[0065]

[Chemical 29]

Synthesis of (3-a) According to the method described in Organic Syntheses Collective Volume III, page 328, m-anisidine (202 g) (3-
a) 147 g were obtained. Synthesis of (3-b) 250 ml of ethanol was added to 74.6 g of (3-a) and dissolved, 0.85 g of 10% palladium carbon was added, and the mixture was contacted with hydrogen for 9 hours in an autoclave. Then, the catalyst was filtered off using Celite as a filter aid, and the filtrate was concentrated (3-
b) 69.1 g were obtained. Synthesis of (3-c) To 63.1 g of (3-b), 252 ml of N, N-dimethylacetamide, 145 g of 3-chloro-1-propanol,
27.1 g sodium hydrogen carbonate, 4 sodium iodide
8.4 g was added and stirring was continued at 100 ° C. for 3 hours. This was poured into water, extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated. This was purified by silica gel column chromatography to obtain (3-c) 82.0 g. Synthesis of (3-d) Methanol 55 was added to 55.4 g of 2,5-dichloroaniline.
4 ml and 142 ml of 12N hydrochloric acid were added, and an aqueous solution in which 23.6 g of sodium nitrite was dissolved was added dropwise with stirring under ice cooling.
During the dropping, the precipitate interfered with stirring, so the mixture was diluted with an appropriate amount of methanol. This is (3-c) 82.
To a suspension obtained by adding 820 ml of methanol and 204 g of sodium acetate to 0 g was added under ice-cooling stirring. Then, this was poured into water and the precipitated crystals were collected by filtration, dissolved in ethyl acetate, washed with saturated brine, dried over sodium sulfate and concentrated, purified by silica gel column chromatography and further recrystallized from acetonitrile (3 -D) 35.3 g was obtained. Synthesis of Exemplified Compound (D-30) (3-d) 35.0 g and 10% Palladium on carbon 0.5 g
Was added to a mixed solvent of 35 ml of ethyl acetate and 35 ml of ethanol and contacted with hydrogen for 2 hours in an autoclave.
Next, the catalyst was filtered off by using Celite as a filter aid, and the filtrate was 26.0 g of 1,5-naphthalenedisulfonic acid tetrahydrate.
Was added dropwise to the methanol solution. The precipitated crystals were collected by filtration to obtain the target compound (D-32), 1.5-naphthalenedisulfonate (37.5 g) as colorless crystals. Melting point 253 [deg.] C-263 [deg.] C (decomposition).

The color developing agent of the present invention can be used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compound to be combined are shown below, but the invention is not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 4-amino-3-methyl-N, N-diethylaniline P-3 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxypropyl) aniline P-4 4-amino-N-ethyl-N- (2-hydroxyethyl) aniline P-5 4-amino-3-methyl-N-ethyl-N-
(2-Hydroxyethyl) aniline P-6 4-amino-3-methyl-N-ethyl-N-
(2-Methanesulfonamidoethyl) aniline P-7 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4- Amino-3-methyl-N-ethyl-N-
(2-Methoxyethyl) aniline P-10 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl) aniline P-11 4-amino-3-methyl-N-ethyl-N-
(2-Butoxyethyl) aniline

Of the above-mentioned p-phenylenediamine derivatives, the compound to be combined is particularly preferably P-3 or P-.
5, P-6 or P-10. Also, these p
-Phenylenediamine derivative and sulfate, hydrochloride, sulfite, p-toluenesulfonate, nitrate, naphthalene-
It is generally used in a salt such as 1,5-disulfonate. In the present invention, the treatment composition may be liquid or solid (for example, powder or granule). Two or more of these compounds can be used in combination depending on the purpose. The amount of the aromatic primary amine developing agent used is preferably 0.001 mol to 1 liter of the color developing solution.
0.2 mol, more preferably 0.005 mol to 0.1
Is a mole.

In the color developing solution of the present invention, compounds which directly retain the aromatic primary amine color developing agent are disclosed in JP-A-63-5341, JP-A-63-106655 and JP-A-4-144446. Various hydroxylamines described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, and phenols described in JP-A-63-54657 and 63-58443. , 63-4
[Alpha] -hydroxyketones and [alpha] -aminoketones described in No. 4656, various sugars described in No. 63-36244, and the like can be contained. In addition, in combination with the above compound, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
3-27841 and 63-25654, etc., monoamines, 63-30845, 63-14.
640, 63-43139 and the like diamines, 63-21647, 63-26655 and 63-46655, and polyamines 63.
No. 53551, Nitroxy Radicals, 63
The alcohols described in -43140 and 63-53549, the oximes described in 63-56654, and the tertiary amines described in 63-239447 can be used. Other preservatives include JP-A-57
Nos. 44148 and 57-53749, various metals, 59-180588, salicylic acids, 54-3582, alkanolamines, and 56-94349, polyethyleneimines. If desired, the aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained.
Especially when hydroxylamines are used, it is preferable to use the above-mentioned alkanolamines and aromatic polyhydroxy compounds in combination. As a particularly preferred preservative, JP-A-3
Hydroxylamines represented by the general formula (I) of No. 144446, and among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferable. The addition amount of these preservatives is 20 mmol to 200 mmol, preferably 30 mmol to 150 mmol, per liter of color developing solution.

Others In the color developing solution of the present invention, various additives described in JP-A-3-144446 can be used. For example, carbonic acid, phosphoric acid, boric acid, hydroxybenzoic acid, etc. of the same patent page (9) can be used as a buffering agent for maintaining pH. It is preferable that the pH of the color developer is maintained at 9.0 to 12.5 by using these buffers. More preferably, it is 9.5 to 11.5. Examples of the antifoggants include halide ions and organic antifoggants described on page (10). In particular, when the concentration of the developing agent in the color developing solution is as high as 20 mmol / liter or higher and when the processing is performed at a high temperature of 40 ° C. or higher, the bromide ion concentration is preferably higher to some extent.
It is preferably 7 mmol / liter or more and 60 mmol / liter or less. If necessary, the halogen can be removed by using an ion exchange resin or an ion exchange membrane to control the concentration within a preferable range. As a chelating agent,
Aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are preferably used. For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-
Compounds typified by N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be used. Further, as a preferable chelating agent, a compound having biodegradability can be mentioned. An example of this is JP-A-63-146998.
No. 63-199295, 63-267.
750, JP-A-63-267751, JP-A-2-2
29146, JP-A-3-186841, German Patent 3
739610, European Patent 468325, etc. are mentioned. Furthermore, development inhibitors such as benzimidazoles, benzothiazoles or mercapto compounds, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, 1-phenyl- An auxiliary developing agent such as 3-pyrazolidone, a viscosity imparting agent, or various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as necessary.

The replenishing amount of the color developing solution of the present invention is preferably 550 ml or less per 1 m ^{2 in} the case of a light-sensitive material for photographing.
450 ml or less is more preferable, 400 ml or less, 80
Most preferred is ml or more. 300 ml by reducing or not containing the bromide ion concentration in the replenisher
It can also be: The processing temperature of the color developing solution is preferably 35 ° C. or higher, more preferably 40 ° C. or higher and 50 ° C. or lower. Further, it is preferable to prevent evaporation of liquid and oxidation of air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below.
That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, and It is preferably 0.0005 to 0.01.
As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
The slit development processing method described in JP-A-63-216050 can be mentioned. Further, it is preferable that the replenishing tank of the color developing solution or the processing solution in the processing layer is shielded with a high boiling point organic solvent or a high molecular compound to reduce the contact area with air. Liquid paraffin and organosiloxane are particularly preferable. Reducing the aperture ratio can be applied not only in both the color development step and the black and white development step, but also in the subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. The developer can be regenerated and used. Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the processing solution called a regenerant is added to increase the activity of the developing solution and to use it again as a processing solution. . In this case, the regeneration rate (ratio of overflow solution in replenisher) is
It is preferably 50% or more, particularly preferably 70% or more. As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in DIAION Manual (I) (14th edition, 1986) issued by Mitsubishi Kasei Co., Ltd. Further, among the anion exchange resins, JP-A-2-952 and JP-A-1-28115 are available.
Resins having the composition described in No. 2 are preferable.

In the present invention, the color-developed light-sensitive material is desilvered. The desilvering process here basically comprises a bleaching process and a fixing process, but it is constituted by combining a bleach-fixing process in which these processes are performed simultaneously and these processes. As the bleaching agent, the above-mentioned JP-A-3-14444 can be used.
As described on page 6 (11), ferric aminopolycarboxylic acid salts or salts thereof are preferably used. For example ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Ferric salts such as 1,3-diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid are listed. In addition, as the bleaching agent, complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are particularly preferable. These aminopolycarboxylic acid iron (III) complex salts are particularly useful in both the bleaching solution and the bleach-fixing solution.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A No. 50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644 and JP-A-53-
94927, 54-35727, 55-265.
No. 06, No. 58-163940; compounds such as bromide ion can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In the desilvering bath of the present invention, in addition to a bleaching agent, a rehalogenating agent, a pH buffering agent and a known additive described on page (12) of JP-A-3-144446 can be used. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acid has an acid dissociation constant (pka) of 2
A compound of formula (6), specifically acetic acid, propionic acid,
Specific examples thereof include hydroxyacetic acid, succinic acid, maleic acid, glutaric acid, fumaric acid, malonic acid, and adipic acid, with succinic acid, maleic acid, and glutaric acid being particularly preferred. The pH of the bleaching solution or the bleach-fixing solution is usually 4.0 to 8.0.
However, in order to speed up the treatment, it is possible to treat at a lower pH.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. It is commonly used, especially ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate with thiocyanate, thioether compound, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and chelating agents such as organic phosphonic acids. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane. Diamine tetraacetic acid, 1,2
Mention may be made of propylenediaminetetraacetic acid. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferable. The fixing solution and the bleach-fixing solution have a pKa of 6.
It is preferable to contain a compound of 0 to 9.0. For example, it is preferable to add imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole in an amount of 0.1 to 10 mol / liter. The imidazole compound represents imidazole and derivatives thereof, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom and the like.
The alkyl group, alkenyl group and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom or the like. The preferred total carbon number of the substituents of the imidazole is 1 to 6, and the most preferred substituent is the methyl group.

Specific examples of the imidazole compound are shown below, but the invention is not limited thereto. Imidazole 1-Methylimidazole 2-Methylimidazole 4-Methylimidazole 4- (2-Hydroxyethyl) -imidazole 2-Ethylimidazole 2-Vinylimidazole 4-Propylimidazole 4- (2-Aminoethyl) imidazole 2,4-Dimethylimidazole 2-Chloroimidazole Among these, preferred compounds are imidazole, 2-methyl-imidazole and 4-methyl-imidazole,
The most preferred compound is imidazole.

When the replenishing system is adopted in the processing of the present invention, the replenishing amount of the fixing solution or the bleach-fixing solution is preferably 100 to 3000 ml, and more preferably 300 to 1800 ml per 1 m ² of the light-sensitive material. The replenishment of the bleach-fixing solution may be conducted as a bleach-fixing replenishing solution, or as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389, an overflow solution of a bleaching solution and a fixing solution is used. May be. In the present invention, the total processing time of the desilvering process consisting of a combination of bleaching, bleach-fixing and fixing is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The treatment temperature is 30 to 60 ° C., preferably 35 to 60 ° C.
55 ° C.

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 the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41, No. 3, issued by Eastman Kodak Company.
The matters described in the 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, and the implementation thereof is described in JP-A-3-33847, No. 8
The contents of the page, upper right column, line 6 to lower left column, line 2
It can be used as is.

The processing solution having fixing ability of the present invention can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. As a silver recovery method,
Electrolysis method (described in French Patent No. 2,299,667),
Precipitation method (JP-A-52-73037, German Patent Nos. 2 and 3)
No. 31,220), an ion exchange method (JP-A-51-1)
7114, German Patent No. 2,548,237) and metal substitution method (UK Patent No. 1,353,805).
Etc. are effective. These silver recovery methods are preferable when they are carried out in-line from the tank solution because the suitability for rapid processing is further improved. Further, the processing solution having a bleaching ability of the present invention can be reused after recovering the overflow solution after use in the processing, adding components to correct the composition. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For playback details,
Fuji Photo Film Processing Manual, Fuji Color Negative Film, C, issued by Fuji Photo Film Co., Ltd.
The matters described on pages 39 to 40 of N-16 processing (revised August 1990) can be applied. The kit for adjusting the processing liquid having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is also small, Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-6-62.
No. 183,461 rotating means to improve the stirring effect, and further, by moving the light-sensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent There are a method of improving the effect and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. 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 the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably 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.

After the processing step having fixing ability, usually,
Perform a washing process. After processing with a processing solution with fixing ability,
It is also possible to use a simple treatment method in which a stabilizing treatment using a stabilizing solution is carried out without substantially washing with water. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows.
e Society of MotionPictureand Tele-vision Enginee
It can be determined by the method described in rs Vol. 64, pp. 248-253 (May 1955 issue). The number of stages is preferably 2 to 4. The replenishing amount is 1 to 50 times, preferably 1 to 30 times, and more preferably 1 to 10 times the amount carried in from the previous bath per unit area. Furthermore, as a method of efficiently reducing the amount of replenishment, divide the washing tank or stabilizing bath with partition walls,
A so-called multi-chamber washing or stabilizing treatment in which the photosensitive material is processed in a liquid without passing through the slit portion of a wiper blade or the like is preferably used.

According to the above-mentioned multi-stage countercurrent method or multi-chamber washing method, the amount of washing water can be greatly reduced. Problems such as adhesion to the material occur. 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. In addition, JP-A-57
-8,542 isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing "Sterilization, sterilization and antifungal technology of microorganisms" edited by the Society for Hygiene Technology (1982) Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal (1986)
It is also possible to use the bactericide described in.

The pH of the washing water and the stabilizing solution in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The temperature and time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally, the range is 20 seconds to 10 minutes at 15 to 45 ° C, and preferably 30 seconds to 5 minutes at 25 to 40 ° C. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834, and JP-A-60-2
All known methods described in No. 20345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, for example, formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

Various surfactants can be contained in the washing water and the stabilizing solution 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.

Various chelating agents are preferably contained in the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are 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 replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
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.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By treating the color negative film and the color paper with the same treatment liquid, the cost of the treatment machine can be reduced and the treatment can be simplified.

The present invention can also be applied to a silver halide photographic light-sensitive material having a transparent magnetic recording layer. Conventionally, in silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials),
The image information is only provided at the time of shooting or printing, but it is not disclosed in JP-A-4-68336 and JP-A-4-73737.
As disclosed in the issue, by providing a transparent magnetic recording layer on the entire surface of the photosensitive material, in addition to the image, the shooting date and time, the weather, the shooting conditions such as reduction / enlargement ratio, the number of reprints, and the portion to be zoomed , Messages, development, print conditions, etc. can be input to the sensitive material, and can also be input to a video device such as a television / video. In that case, it is desired to remove the influence of dust due to electrification, improve the slipperiness of the film, and eliminate the influence of curl containing the support.

These will be described in detail below. The magnetic particles that can be used in the present invention are ferromagnetic iron oxides such as γ-Fe ₂ O ₃ (FeOx, 4/3 <x ≦ 3/2), Co-deposited γ-F.
Co-coated ferromagnetic iron oxide such as _{e 2 O 3 (FeOx, 4} /3
<X ≦ 3/2), Co-deposited magnetite, other Co-containing ferromagnetic iron oxides, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metals, ferromagnetic alloys, and other ferrites such as hexagonal Ba Ferrite, Sr ferrite, Pb ferrite, Ca ferrite, or a solid solution or ion substitution product of these can be used, but it is a Co-deposited ferromagnetic iron oxide such as Co-deposited γ-Fe ₂ O ₃ and Fe.
^{A 2 +} / Fe3 ⁺ ratio of 0 to 10% is preferable from the viewpoint of transmission density.

The shape of the ferromagnetic material may be needle-like, rice grain-like, spherical, cubic or plate-like, but needle-like is preferable in terms of electromagnetic conversion characteristics. In the case of needle-like particles, the major axis is 0.01 to 0.8 μm, and the major axis / minor axis ratio is 2-1.
00, more preferably 0.05 to 0.3 μm in the major axis and more preferably 4 to 15 in the major axis / minor axis ratio. S in specific surface area
_{The BET} is preferably 20 m ² / g or more, and more preferably 30 m ² / g or more. The larger the saturation magnetization (σs) of the ferromagnetic material, the more preferable, but 50 emu / g or more, more preferably 70 em.
u / g or more, and practically 100 emu / g or less. The squareness ratio (σr / σs) of the ferromagnetic material is preferably 40% or more, more preferably 45% or more. If the coercive force (Hc) is too small, it will be easily erased, and if it is too large, it will not be possible to write depending on the system, so an appropriate value is preferable.
e or more and 3000 Oe or less, preferably 500 Oe or more 2
000 Oe or less, more preferably 650 Oe or more 95
It is 0 Oe or less.

These ferromagnetic particles are described in, for example, Japanese Patent Laid-Open No.
It may be surface-treated with silica and / or alumina such as those described in JP-A-9-23505 and JP-A-4-096052. Further, JP-A-4-195726, JP-A-4-192116, JP-A-4-259911, and JP-A-5-0.
Surface treatment with an inorganic and / or organic material as described in No. 81652 may be applied. Furthermore, these ferromagnetic particles may be treated on their surface with a silane coupling agent or a titanium coupling agent. Next, the binder in which the magnetic particles of the present invention are preferably used will be described.
The binder used in the present invention is a known thermoplastic resin conventionally used as a binder for magnetic recording media, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, Natural product polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The preferred Tg of the above resin is -40 ° C or higher.
The temperature is 300 ° C. and the weight average molecular weight is 20,000 to 1,000,000, preferably 5,000 to 300,000.

Among the binders, cellulose di (or tri) acetate is preferred. The binders may be used alone or as a mixture of several kinds, and a known crosslinking agent of epoxy type, aziridine type, isocyanate type and / or a radiation curable vinyl type monomer may be added for curing treatment. Particularly preferred are isocyanate cross-linking agents, such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and reaction products of these isocyanates with polyalcohols (for example, 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane). Reaction products), and polyisocyanates produced by condensation of these isocyanates. As the cross-linking agent having an epoxy group, for example, a trimethylolpropane triglycidyl adduct or a pentaerythritol tetraglycidyl adduct is preferable. The radiation-curable vinyl-based monomer is a compound that can be polymerized by irradiation with radiation, and is preferably diethylene glycol di (meth) acrylate having two or more (meth) acryloyl groups,
Polyethylene glycol (meth) acrylates, such as triethylene glycol di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, reaction product of polyisocyanate and hydroxy (meth) acrylate compound, etc. There is. These cross-linking agents are preferably 5 to 45 wt% with respect to the total binder containing the cross-linking agents.

A hydrophilic binder can also be used in the magnetic recording layer, and water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. As the latex polymer, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer,
Examples thereof include acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Of these, gelatin is the most preferable. Examples of hardeners for gelatin include 2-hydroxy-4,6-dichloro-1,3,5-triazine, divinyl sulfone, isocyanates described in US Pat. No. 3,103,437, and the like. US Pat. Nos. 3,017,280 and 2,9
Examples thereof include aziridine compounds described in U.S. Pat. No. 83,611 and carboxyl group-activating type hardeners described in U.S. Pat. No. 3,321,313. The amount of hardener used is usually 0.01 to 3 with respect to dry gelatin.
It is 0% by weight, preferably 0.05 to 20% by weight.

Various known means can be used to disperse the above-mentioned magnetic material in the binder, but a kneader, a pin type mill, an annular type mill or the like is preferable, and the kneader and the pin type mill or the kneader is used. A combined use of an annular mill is also preferable. The thickness of the magnetic recording layer is 0.1 μm
It is 10μ, preferably 0.2μ to 5μ, and more preferably 0.3μ to 3μ. The weight ratio of magnetic particles to binder is preferably comprised between 0.5: 100 and 60: 100,
More preferably, it is 1: 100 to 30: 100. The coating amount of the magnetic material is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , and more preferably 0.02 to 0.
5 g / m ² .

The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in the form of a stripe. The method for applying this magnetic recording layer includes air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat, dip coat, bar. A coat, an extrusion coat, etc. can be used, and other methods are also possible, and detailed explanations of these can be found in "Coating Engineering", page 253, published by Asakura Shoten.
It is described in detail on page 277 (published 46.20. Showa). The magnetic recording layer may have functions such as lubricity improvement, curl control, antistatic, adhesion prevention and head polishing, or may be provided with another functional layer to impart these functions. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance. For example, inorganic or organic fine particles (eg, silica, SiO ₂ , SnO) may be used.
₂ , Al ₂ O ₃ , TiO ₂ , crosslinked polymethylmethacrylate, barium carbonate, fine silicone particles, etc.) are preferably added.

In the light-sensitive material of the present invention, a polyethylene aromatic dicarboxylate type polyester support is preferable as the support. Here, the polyester is formed with a diol and an aromatic dicarboxylic acid as essential components, but dibasic acids that can often be used as a mixture with other dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, and phthalic anhydride. , Naphthalenedicarboxylic acid (2,6-, 1,5
-, 1,4-, 2,7-), diphenylene-p, p'-
Dicarboxylic acid, tetrachlorophthalic anhydride, succinic acid,
Glutaric acid, adipic acid, sebacic acid, succinic anhydride,
Maleic acid, fumaric acid, maleic anhydride, itaconic acid,
Citraconic anhydride, Tetrahydrophthalic anhydride, 3,6
-Endomethylene tetrahydrophthalic anhydride, 1,4-
Cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1,
1-dicarboxy-2-phenyl ethylene, 1,4-
Examples thereof include dicarboxymethylphenol, 1,3-dicarboxy-5-phenylphenol, and sodium 3-sulfoisophthalate. The essential aromatic dicarboxylic acid is one having at least one benzene nucleus among the above-mentioned dicarboxylic acids.

Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1 Examples thereof include cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, p-hydroxyethyloxybenzene (PHBA), and bisphenol A. If necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester of the present invention may be salicylic acid or the like, which may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule.

Preferred as the polymer formed is
Homopolymers such as polyethylene terephthalate, polyethylene naphthalate and polycyclohexanedimethanol terephthalate (PCT), and copolymers of terephthalic acid, naphthalenedicarboxylic acid and ethylene glycol (the mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 0.9: 0. 1 to 0.1: 0.9 is preferable,
It is more preferably 0.8: 0.2 to 0.2: 0.8. ) Is preferred. Particularly preferred is a polyester containing 2,6-naphthalenedicarboxylic acid. Specifically, 2,6-
It is a polyester containing 0.1 to 1.0 of naphthalene dicarboxylic acid. Among them, polyethylene is particularly preferable.
It is 2,6-naphthalate.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters, and for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition".
(Kyoritsu Shuppan, 1980) 103-136.
The description can be made with reference to the description on pages 187 to 286 of "Synthetic Polymer V" (Asakura Shoten, 1971). The preferred average molecular weight range for these polyesters is about 500.
It is 0 to 200,000. In addition, these polyesters may be partially blended with another polyester to improve adhesion with another type of polyester,
It is possible to copolymerize a monomer constituting another polyester, or to copolymerize a monomer having an unsaturated bond in these polyesters and radically crosslink them. Polymer blends obtained by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482 and JP-A-6-5482.
4-4325, JP-A-3-192718, Research Disclosure 283, 739-41, 28
It can be easily formed according to the method described in Nos. 4,779-82 and 294,807-14.

Polyester has a Tg of 50 ° C. or higher, but the conditions of use are not generally handled with sufficient caution, and the temperature is often exposed to 40 ° C. especially in the midsummer outdoors. From this point of view T
From the viewpoint of safety, g is preferably 55 ° C. or higher. More preferably, Tg is 60 ° C. or higher, particularly preferably 70.
℃ or above. Further, it is preferable that Tg is 90 ° C. or higher in order to complete the treatment. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used by general users, that is, the temperature in summer exceeds 40 ° C. Polyesters having a glass transition temperature above the temperature are preferred.

Next, examples of preferable specific compounds of the polyester which can be used in the present invention are shown, but the present invention is not limited thereto. Polyester compound example P-0: [Terephthalic acid (TPA) / ethylene glycol (EG) (100/100)] (PET) Tg = 80 ° C. P-1: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene Glycol (EG) (100/100)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: [TPA / Bisphenol A (BPA) (100/100)] Tg = 192 ° C

P-4: 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C P-7: TPA / EG / BPA (100/50/50) Tg = 105 ° C P -8: TPA / EG / BPA (100/25/75) Tg = 135 ° C. P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C.

P-10: Isophthalic acid (IPA) / NDCA / TPA / EG (20/50/30/100) Tg = 95 ° C. P-11: NDCA / Neopentyl glycol (NPG) / EG (100/70 / 30) Tg = 105 ° C. P-12: TPA / EG / bisphenol (BP) (100/20/80) Tg = 115 ° C. P-13: PHBA / EG / TPA (200/100/100) Tg = 125 ° C. P -14: PEN / PET (60/40) Tg = 95 ° C. P-15: PEN / PET (80/20) Tg = 104 ° C. P-16: Polyarylate (PAr) / PEN (50/50) Tg = 142 ° C P-17: PAr / polycyclohexane dimethanol terephthalate (PCT) (50/50) Tg = 118 ° C P-18: PAr / PET (60/40) Tg = 10 ° C P-19: PEN / PET / PAr (50/25/25) Tg = 108 ° C P-20: TPA / 5-sulfoisophthalic acid (SIP) / EG (95/5/10 0) Tg = 65 ° C P-21: PEN / SIP / EG (99/1/100) Tg = 115 ° C

These supports are 50 μm or more and 300 μm or more.
It has a thickness of m or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying.
If it exceeds μm, it is inconsistent with the purpose of reducing the thickness for compactness. More preferably, the thickness is preferably 50 to 200 μm from the strength of the waist, and further 8
0 to 115 μm is preferable, and 85 to 10 is particularly preferable.
It is 5 μm. In the present invention, the polyester support is preferably subjected to a heat treatment, in which case the temperature is 40 ° C.
It is necessary to perform the treatment at a temperature not higher than the glass transition temperature for 0.1 to 1500 hours, which results in a film that is hard to curl. More preferably, it is a heat treatment at Tg of -20 ° C or higher and lower than Tg. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1 to −5 ° C./hour. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. If the time is 0.1 hours or less, a sufficient effect cannot be obtained, and if the time is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. In order to further increase the effect of eliminating the curl, the heat treatment is performed at a temperature of Tg or higher and lower than the melting point (melting temperature determined by DSC) before this heat treatment to erase the heat history of the support, and then the above 40 It is preferable to perform the heat treatment again at a temperature of ℃ or more and less than Tg.

The heat treatment of such a support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web. When the heat treatment is carried out in the form of a roll, it may be carried out by any of a method in which the roll is heat-treated from room temperature in a constant temperature bath, and a method in which the roll is wound into a roll after being heated to a predetermined temperature during web conveyance. In the heat treatment in a roll, due to the heat shrinkage stress generated during the heat treatment, surface defects such as wrinkles due to winding tightness and cut-out of the core portion are likely to occur.
For this reason, unevenness is added to the surface (for example, conductive inorganic fine particles such as SnO ₂ / Sb ₂ O ₅ or colloidal silica is applied) to reduce creaking between the supports to prevent wrinkles due to winding tightening. It is desirable to take measures such as preventing the cut edge of the winding core from being exposed by giving a knurl to the end of the support and slightly raising only the end. When the heat treatment is performed in the form of a web, a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the form of a roll. These heat treatments may be carried out at any stage after the support film formation, the glow discharge treatment, the back layer application (antistatic agent, slip agent, etc.), and the undercoat application. Preferred is after the antistatic agent is applied. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment.

Next, in the present invention, regarding the polyester, in order to further enhance its function as a photographic support,
It is preferable to coexist with various additives. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber does not have absorption in the visible region, and the addition amount thereof is usually 0.01 to 20% by weight, preferably 0.05 to 10% by weight based on the weight of the polyester film. %. 2,4-dihydroxybenzophenone as an ultraviolet absorber, 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenone-based compounds such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-
Examples thereof include benzotriazole-based UV absorbers such as 3′-di-t-butyl-5′-methylphenyl) benzotriazole and salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

Further, in order to avoid the light piping phenomenon, it is preferable to add inert inorganic particles or the like to the support, and it is preferable to add a dye. The dye is not particularly limited, and examples of the dye include those manufactured by Mitsubishi Kasei. Diares
In, it is possible to achieve the object by mixing dyes commercially available for polyester such as Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more. The polyester film according to the present invention can be imparted with slipperiness according to the use, and SiO ₂ , TiO ₂ , Ba as the inert inorganic particles.
SO ₄ , CaCO ₃ , talc, kaolin, etc. are added.

When any of these polyester films is used as a support, since each of these polyester supports has a hydrophobic surface, a photographic layer (for example, a photosensitive halogen) containing a protective colloid mainly containing gelatin is provided on the support. It is preferable to perform various surface treatments in order to firmly adhere the silver halide emulsion layer, the intermediate layer, the filter layer, etc.). Examples thereof include surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. After these surface treatments, an undercoat layer may be provided or a photographic emulsion layer may be directly coated.

Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. First, the ultraviolet irradiation treatment will be described below. These are Japanese Examined Patent Publication Nos. 43-2603, 43-2604, and 4
It is preferably carried out by the treatment method described in No. 5-3828. A high-pressure mercury lamp consisting of a mercury lamp and a quartz tube, which has an ultraviolet wavelength of 180 to 320 nm, is preferred. The UV irradiation may be performed in the stretching step of the support, at the time of heat setting, or after the heat setting. If there is no problem in the performance of the support that the surface temperature of the support is increased to around 150 ° C., a high pressure mercury lamp having a main wavelength of 365 nm can be used. When low temperature processing is required, the dominant wavelength is 254 nm
Low pressure mercury lamps are preferred. It is also possible to use an ozone-less type high pressure mercury lamp and a low pressure mercury lamp.

Next, the corona discharge treatment will be described. Any conventionally known method, for example, Japanese Patent Publication No. 48-5043,
47-51905, JP-A-47-28067, 49-83767, 51-41770 and 51-.
It can be achieved by the method disclosed in No. 131576 or the like. The discharge frequency is suitably 50 Hz to 5000 KHz, preferably 5 KHz to several hundred KHz, and particularly preferably 10 Hz to 30 KHz. Regarding the processing strength of the object to be processed, it is usually 0.001 KV · A · min / m ² ~
5 KV · A · min / m ² , preferably 0.01 KV · A · min / m ²
Appropriate values are ~ 1 KV · A · min / m ² . The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm. Corona discharge treatment machine
A Pillar solid state corona processor 6KVA model can be used. Further, as the flame treatment, natural gas, liquefied propane gas, etc. can be used, and the mixing ratio with air is important. The preferred gas / air mixing ratio is by volume,
For propane, 1/14 to 1/22, more preferably 1 /
It is 16 to 1/19. 1/6 to 1/1 for natural gas
It is 0, more preferably 1/7 to 1/9. The flame treatment amount is 1 to 50 Kcal / m ² , and more preferably 3 to 20 Kcal / m ² .
m ² . It is also effective to set the distance between the tip of the internal flame of the burner and the support to less than 4 cm.

The glow discharge treatment is carried out by any conventionally known method, for example, Japanese Examined Patent Publication Nos. 35-7578 and 36-1.
No. 0336, No. 45-22004, No. 45-2200
No. 5, No. 45-24040, No. 46-43480,
US Pat. Nos. 3,057,792 and 3,057,795
Issue 3, Issue 3,179,482, Issue 3,288,638
No. 3,309,299, No. 3,424,735
No. 3, 3,462,335, 3,475,307
No. 3,761,299, British Patent 997,093
JP-A No. 53-129262 and the like can be used. There is a method of introducing various gases such as oxygen, nitrogen, helium or argon into the atmosphere of glow discharge treatment, but glow discharge treatment in the presence of water vapor is preferable. The steam partial pressure is preferably 10% or more and 100% or less, and more preferably 40% or more and 90% or less. 10
If it is less than%, it becomes difficult to obtain sufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like. Further, it is preferable to preheat the film to be surface-treated, preferably 50 ° C. or higher and Tg or lower, and 70 ° C. or higher Tg.
The following is more preferable, and 90 ° C. or higher and Tg or lower is further preferable. As a method of raising the surface temperature of the support in vacuum,
There are heating by an infrared heater, heating by contact with a hot roll, and the like.

The pressure during glow discharge treatment is 0.005 to 2
It is preferably 0 Torr. More preferably 0.02-
2 Torr. Further, the voltage is preferably between 500 and 5000V. More preferably, it is 500-3000V. The discharge frequency used is, as seen in the prior art, from direct current to several 1000 MHz, preferably 50 Hz to.
20 MHz, more preferably 1 KHz to 1 MHz. Discharge treatment intensity is 0.01 KV · A · min / m ^{2 to 5} KV ·
A · min / m ² is preferable, more preferably 0.15 KV · A
Desired adhesive performance at · min / m ² ~1KV · A · min / m ^2. It is preferable that the temperature of the support thus subjected to the glow discharge treatment is immediately lowered by using a cooling roll.

Next, the method of undercoating the surface-treated support will be described. Single layer or multiple layer method may be used, such as vinyl chloride,
Starting with copolymers starting from monomers selected from vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethyleneimine, epoxy resins, grafted gelatin, nitro For many polymers such as cellulose, a binder based primarily on gelatin is preferred for the second subbing layer in the overlay. Examples of the undercoat polymer include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol,
Examples thereof include polyacrylic acid copolymers and maleic anhydride copolymers, and examples of cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose.
As the latex polymer, a vinyl chloride-containing copolymer,
Examples thereof include vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support which can be used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichloro. Examples include phenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), epichlorohydrin resin And so on.

The undercoat layer of the present invention includes SiO ₂ , TiO ₂ ,
Inorganic particles such as a matting agent or polymethylmethacrylate copolymer particles (1 to 10 μm) can be contained as a matting agent. The undercoat liquid is generally well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. No. 2,681,294. It can be applied by an extrusion coating method using a hopper described in the manual. If desired, U.S. Pat. No. 2,761,791,
Nos. 3,508,947, 2,941,898, and 3,526,528, Yuji Harasaki, "Coating Engineering", page 253 (1973, published by Asakura Shoten).
Two or more layers can be simultaneously coated by the method described in the above. In the present invention, it is preferred that the support is heat-treated with polyethylene-2,6-naphthalenedicarboxylate for 24 hours between 100 ° C. and 115 ° C. and the thickness of the support is 85 μm-105 μm. It has been subjected to ultraviolet irradiation treatment or glow discharge treatment, and the back side non-photosensitive hydrophilic layer is 1 to 7 μm.
The gelatin layer and the non-photosensitive hydrophilic layer is 0.5 to
It is characterized in that it is a cellulose binder of 5 μm. At this time, the weight ratio of the gelatin amount of the non-photosensitive hydrophilic layer of the back layer to the gelatin layer of the emulsion layer on the opposite side was 0.1.
~ 0.5 is preferred.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be black or white or color. Here, a color silver halide photographic light-sensitive material will be described. The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. 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 light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged 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. In the installation, each layer may be sequentially coated, or the coating may be performed in a single layer (so-called simultaneous multilayer coating), which is a manufacturing method which is quite common in the art, and is not particularly specified.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
The couplers and DIR compounds as described in JP-A 1-20037 and JP-A 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-112751.
No. 62-200350, No. 62-206541.
No. 62-206543, No. 56-25738,
62-63936, 59-202464, JP-B-55-34932, and 49-15495.

The silver halide grains include those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, twin planes and the like. It may have a crystal defect or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, 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 (RD) No. 1764.
3 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 1 thereof.
8716 (November 1979), p.648, "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Monte
, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, PhotographicEmulsion Chemist
ry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZelikman e
t al., Making and Coating Photographic Emulsion, F
Ocal Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable. Further, tabular grains having an aspect ratio of about 5 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), 14th
Volume 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be easily prepared by the method described in 33,048, 4,439,520 and British Patent 2,112,157. Even if the crystal structure is uniform,
The inside and the outside may have different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles having various crystal forms may be used. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such processes are Research Disclosure No. 17643 and No. 17643.
18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the related portions are shown in the following table. (Types of Additives) (RD17643) (RD18716) 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to page 648, right column to page 649 Right column 4 Whitening agent 24 pages 5 Antifoggants, and safety 24 to 25 pages 649 Right column to constant agent 6 Light absorbers, filter dyes 25 to 26 pages 649 Right column to 650 left columns Materials, UV absorption Agent 7 Anti-staining agent Page 25 Right column Page 650 Left-right column 8 Dye image stabilizer Page 25 9 Hardener 26 page 651 Page left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant 27 page 650 Right column 12 Coating Aids, Surfactants, pages 26 to 27, page 650, right column In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,987 and US Pat. It is preferred to add to the light-sensitive material a compound capable of fixing by reacting with the formaldehyde described.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. . Examples of the yellow coupler which can be used in combination with the yellow coupler of the present invention include, for example, U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024 and 4 , 401, 752, and 4, 248, 961,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
511,649, 5,066,576, 4,476,219, European Patent 249,473A.
No. 502,424A, No. 513,496A
No. 498, 381A No. 447, 969A No.
And those described in JP-A-5-307248 and 4-274425.

As magenta couplers, US Pat. Nos. 4,310,619, 4,351,897, EP 73,636, 456,257, 486,965 and US Patent No. 3,061,432,
No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-
33552, Research Disclosure No. 24
230 (June 1984), JP-A-60-43659.
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Pat. No. 4,500,630, No. 4,540,654.
No. 4,556,630, WO (PCT) 88 /
04795, JP-A-3-39737 and 6-436.
No. 11, No. 5-204106, No. 4-362631 and the like are preferable.

As cyan couplers, US Pat.
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334, 011, No. 4,327, 1
73, West German Patent Publication No. 3,329,729, European Patents 121,365A, 249,453A, U.S. Patents 3,446,622, 4,433,99.
No. 9, No. 4,753, 871, No. 4,451, 5
No. 59, No. 4,427, 767, No. 4,690,
889, 4,254,212 and 4,29
6,199, JP-A-61-42658, JP-A-4-
No. 204843, No. 4-43345, No. 6-6738
Those described in No. 5 and the like are preferable. Of these, 2 equivalents of a naphthol-based coupler is most preferable because it has high reactivity with an oxidized product of a color developing agent and can form a dye with a small amount of an oxidized product of a color developing agent.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No.
17643, Section VII-G, U.S. Pat. No. 4,163,67
No. 0, Japanese Examined Patent Publication No. 57-39413, US Pat.
4,929, 4,138,258, and 4,8
37,136, 4,833,069, British Patent 1,146,368, European Patent Publication 456,25.
Those described in No. 7 are preferable. Examples of the coupler in which the color forming dye has excessive diffusibility include US Pat. No. 4,366,2.
37, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) 3,234,53.
Those described in No. 3 are preferable. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,820.
No. 4,009,211, No. 4,367,28
No. 2, No. 4,409,320, No. 4,576,9
No. 10, British Patent No. 2,102,137, JP-A-2-
No. 44345 and the like. Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII-F patents, JP-A-57-151944, and JP-A-57-15.
No. 4234, No. 60-184248, No. 63-373.
46, JP-A-5-307248, U.S. Pat. No. 4,2.
48,962, European Patent Nos. 378,236 and 4
Those described in Nos. 36,938 and 440,195A2 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, there is described in British Patent No. 2,093.
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
-185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252 and the like, and after separation as described in EP 173,302A Couplers that release dyes that recolor, R.I. D. No. 11449, 24
No. 241, bleaching accelerator releasing coupler described in JP-A No. 61-201247, and a ligand-releasing coupler described in US Pat. No. 4,553,477, JP-A-63-75.
Examples thereof include couplers releasing the leuco dye described in No. 747.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, Examples thereof include alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives and hydrocarbons. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide. The process of latex dispersion method, effects and specific examples of latex for impregnation are described in US Pat.
199,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less,
Moreover, the film swelling speed T _1/2 is preferably 30 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr.Sci.En) by A. Green et al.
g.), 19 vol., No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. in a color developing solution, 3 minutes 15 seconds 90% of the maximum swollen film thickness reached upon treatment is defined as the saturated film thickness, and is defined as the time required to reach this film thickness of T _1/2 .

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness. Further, in the present invention, materials used for various silver halide photographic light-sensitive materials can be used. Further, in the present invention, an antistatic agent is preferably used. The antistatic agent is not particularly limited, and examples thereof include a carboxylic acid and a carboxylic acid salt as the anionic polymer electrolyte,
A polymer containing a sulfonate is disclosed in, for example, JP-A-48-220.
17, JP-B-46-24159, JP-A-51-30
725, JP-A-51-129216, JP-A-55-
It is a polymer as described in No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
3, JP-A-48-91165, JP-B-49-245.
No. 82 is available. Further, the ionic surfactant has anionic property and cationic property, and is disclosed in, for example, JP-A-49-85826 and JP-A-49-33630.
U.S. Pat. No. 2,992,108, U.S. Pat. No. 3,2
06, 312, JP-A-48-87826, JP-B-4
Examples thereof include compounds described in JP-A-9-11567, JP-B-49-11568 and JP-A-55-70837.

The most preferable antistatic agent is Z.
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ ,
At least one crystalline metal oxide selected from SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ or a composite oxide thereof (Sb, P, B, In, S, Si,
C) and further, sol-like metal oxides or fine particles of composite oxides thereof. The fine particles or acicular filler of the conductive crystalline oxide or its composite oxide used in the present invention has a volume resistivity of 10 ⁷ Ω-cm or less, more preferably 10 ⁵ Ω-cm or less. The particle size is 0.001 to 1.0 μm, especially 0.001.
It is desirable to set the thickness to 0.3 μm. In order to give conductivity more efficiently, the primary fine particles are partially aggregated to 0.0
It is preferable to use fine particles or filler of a conductive crystalline oxide or a composite oxide thereof having a particle size of 1 to 0.2 μm.
Further, the conductivity reached when producing an antistatic layer using these is preferably 10 ¹² Ω or less, more preferably 10 ¹⁰ Ω, both in the raw and after-treated electrical resistances.
Hereafter, it is particularly preferable that the electric resistance is 10 ^9.5 Ω or less. In that case, the content in the photosensitive material is generally 5 to 5.
00 mg / m ² is preferred, particularly preferably 10-350 mg
/ M ² . The amount of the binder is 1 to 500 mg / m ²
Is preferred, and especially 5 to 300 mg / m ² is preferred. The ratio of the amount of fine particles of conductive crystalline oxide or composite oxide thereof or acicular filler to binder is 1/300 to 100 /
1 is preferable, and more preferably 1/100 to 100/5.
Is.

The light-sensitive material of the present invention preferably has slipperiness. The slipperiness is good on both the photosensitive layer surface and the back surface, but the back surface is more effective. A preferable sliding property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when moving at 60 cm / m ² with respect to a stainless ball having a diameter of 5 mm. In this evaluation, even if the surface of the photosensitive layer is replaced as the mating material, the values are almost the same. Examples of slips that can be used in the present invention include polyorganosiloxanes disclosed in JP-B-53-292, and higher fatty acids disclosed in U.S. Pat. No. 4,275,146. Amide, Japanese Patent Publication No. 58-33541, British Patent No. 927,446, or JP-A-55.
-126238 and 58-90633, higher fatty acid ester (having 10 to 2 carbon atoms) as disclosed in
Ester of fatty acid of 4 and alcohol having 10 to 24 carbon atoms),
And higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, and JP-A-58-58
Esters of linear higher fatty acids and linear higher alcohols, as disclosed in 50534, WO 90,10.
A higher fatty acid-higher alcohol ester containing a branched alkyl group as disclosed in JP8,115.8 is known.

The higher fatty acids and their derivatives and the higher alcohols and their derivatives include higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides,
Polyhydric alcohol esters of higher fatty acids, etc., higher aliphatic alcohols, monoalkyl phosphites of higher aliphatic alcohols, dialkyl phosphites, trialkyl phosphites, monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, higher alkyls Aliphatic alkyl sulfonic acid, its amide compound, its salt, etc. can be used. The slip agent used in the present invention can be dispersed in an organic solvent by various methods. As a method of dispersing in an organic solvent, a lubricant is solid-dispersed in an organic solvent with a ball mill, a sand grinder, or the like, a lubricant is dissolved by heating in an organic solvent, and cooling precipitation is performed while stirring. Dispersion method, or a method in which a lubricant is dissolved in an organic solvent by heating and then added to an organic solvent at room temperature or in a cooled state to disperse by cooling and precipitation, and mutually compatible. Not emulsifying with organic solvents. As the disperser used, an ordinary stirrer can be used, but an ultrasonic disperser and a homogenizer are particularly preferable.

Next, the film cartridge used in the present invention will be described. The patrone used in the present invention may be a conventional metallic patrone for 135, or may be made of synthetic plastic as a main material. As the plastics material, polystyrene, polyethylene, polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, methylmethacryl resin, There are vinyl formal resin, vinyl butyral resin, polyethylene terephthalate, Teflon, nylon, phenol resin, melamine resin and the like.

The cartridge may contain various antistatic agents. The antistatic agent is not particularly limited, but carbon black, metal oxide particles, nonion, anion, cation and betaine-based surfactants or polymers can be preferably used. As these antistatic patrones, JP-A Nos. 1-312537 and 1-3125 are available.
No. 38. The size of the patrone may be the same as it is or the current diameter of the cartridge of 25 m / m is 2
It is effective to reduce the size of the camera by setting it to 2 m / m or less, preferably 20 m / m or less and 14 m / m or more. Also, US Patent No. 4,
834,306 (corresponding to JP-A-1-306845)
Film cartridge disclosed in Japanese Patent Laid-Open No. 4-11
The film patrone disclosed in US Pat. No. 5,251, US Pat. No. 5,226,613 can also be used. These film cartridges may be so-called raw films before development, or may be developed photographic films. Further, the raw film and the developed photographic film may be housed in the same new cartridge, or may be different cartridges.

[0137]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. 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. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, 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 0.18 Gelatin 1.40 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.030 UV-1 0.020 UV-2 0.020 UV-3 0.060 HBS-1 0.05 HBS-2 0.020 Polyethyl acrylate latex 0.080 Gelatin 0.90

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.19 Emulsion B Silver 0.19 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.050 ExC-3 0.030 ExC-4 0.14 ExC-5 3.0 x 10 ^-3 ExC-7 1.0 x 10 ^-3 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.10 Gelatin 1.00

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.60 ExS-1 3.4 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.050 ExC-5 0.010 ExC-8 0.010 Cpd-2 0.023 HBS-1 0.11 Gelatin 0.60

Fifth Layer (High Sensitive Red Sensitive Emulsion Layer) Emulsion D Silver 1.54 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.10 ExC-3 0.050 ExC-5 2.0 × 10 ^-3 ExC-6 0.010 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.20 HBS-2 0.10 Gelatin 1.30 6th layer (intermediate layer) Cpd-1 0.090 HBS-1 0.05 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 0.24 Emulsion F Silver 0.24 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 5.0 × 10 ^-3 ExM-2 0.28 ExM-3 0.086 ExM-4 0.030 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.85

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion G Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.14 ExM-3 0.045 ExM-5 0.020 ExY-1 8.0 × 10 ^-3 ExY-3 0.020 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion H Silver 1.29 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 0.050 ExM-5 0.020 ExY-1 4.0x10 ^-3 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 1.45

10th layer (yellow filter layer) Yellow colloidal silver Silver 7.5 × 10 ^-3 Cpd-1 0.13 Cpd-4 7.5 × 10 ^-3 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion I Silver 0.25 Emulsion J Silver 0.25 Emulsion K Silver 0.10 ExS-7 8.0 × 10 ^-4 ExC-7 0.010 ExY-1 0.02 ExY-2 0.90 HBS- 1 0.25 gelatin 1.62

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion L Silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.20 ExY-1 4.0 × 10 ^-3 Cpd-2 0.10 HBS-1 0.050 Gelatin 1.10

Thirteenth layer (first protective layer) UV-2 0.10 UV-3 0.12 UV-4 0.30 HBS-1 0.10 Gelatin 2.50

14th layer (second protective layer) Emulsion M Silver 0.10 H-1 0.32 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 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 are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt. Cpd-4 was dispersed in a solid state according to the method described in International Patent No. 88-4794.

[0152]

[Table 1]

In Table 1, (1) Emulsions I to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to L were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) In the tabular grains, dislocation lines as described in JP-A-3-237450 are observed using a high voltage electron microscope.

The couplers and additives in each layer were dispersed in a gelatin solution by the method shown in Table 2. The addition method for each layer is shown in Table 3.

[0155]

[Table 2]

[0156]

[Table 3]

[0157]

Embedded image

[0158]

[Chemical 31]

[0159]

Embedded image

[0160]

[Chemical 33]

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

[Chemical 38]

[0166]

[Chemical Formula 39]

[0167]

[Chemical 40]

[0168]

Embedded image

[0169]

Embedded image

[0170]

[Chemical 43]

[0171]

[Chemical 44]

Sample 102 was prepared in exactly the same manner except that the yellow couplers (ExY-1, ExY-2) of the 11th and 12th layers of Sample 101 were changed in equimolar amounts to the couplers of the present invention shown in Tables 4 to 6. ~ 111 were produced.

The samples 101, 102, and 103 were subjected to wedge exposure with white light, and a running process was performed using an automatic developing machine until the replenishment amount of the color developing solution became three times the volume of the tank. Then, an experiment as described later was conducted. The treatment process and the treatment liquid composition are shown below.

(Processing method) Process processing time Processing temperature Replenishment amount ^* Tank capacity Color development 1 minute 30 seconds 38.0 ℃ 600ml 5 liters Bleach 50 seconds 38.0 ℃ 130ml 1 liter Bleach fixing 50 seconds 38.0 ℃ -1 liter Fixed 50 seconds 38.0 ℃ 420ml 1 liter water wash 30 seconds 38.0 ℃ 880ml 0.6 liter stable (1) 20 seconds 38.0 ℃ − 0.6 liter stable (2) 20 seconds 38.0 ℃ 520ml 0.6 liter dry 1 minute 30 seconds 60 ℃ The stabilizing solution per 1 m ² was a countercurrent method from (2) to (1), and the overflow solution of washing water was all 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 developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. 70 ml,
It was 60 ml, 60 ml and 60 ml. The crossover time is 6 seconds in all cases, 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 3.2 4.2 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg disodium-N, N-bis (sulfonate ethyl) hydroxylamine 2.0 3.0 hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] -aniline (ExD- 1) Sulfate (developing agent) 16 mmol 20 mmol Water added 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ferric Ammonium Monohydrate 130 195 Ammonium Bromide 70 105 Ammonium Nitrate 14 21 Hydroxyacetic Acid 25 38 Acetic Acid 40 60 1.0 liter by adding water 1.0 liter pH (adjusted with ammonia water) 4.6 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
H 7.0)

(Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 liter 840 liter Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water added 1.0 liter 1.0 liter pH (Adjust with ammonia water and acetic acid) 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg /
Treat to less than 1 liter, followed by 20 mg sodium isocyanurate dichloride / liter and 150 mg sodium sulfate
/ Liter was added. The pH of this liquid is 6.5 to 7.5.
Was in the range.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (Unit: g) Sodium P-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid diester Sodium salt 0.05 1,2-benzisothiazolin-3-one 0.03 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water to 1.0 liter pH 8.5

Further, the developing agent ExD- in the color developing solution is used.
1 was changed to each developing agent shown in Tables 4 to 6 in an equimolar amount, and the same processing was performed.

After processing, the cyan and yellow characteristic curves of each sample were measured with red and blue light. (Evaluation of lower layer developability) The relative sensitivity (S _0.2 (R)) represented by the logarithm of the reciprocal of the exposure amount giving the cyan (R) density (Dmin + 0.2) was determined from the obtained characteristic curve. S
_The larger the value of _0.2 (R), the better the developability of the lower layer and the more suitable the image forming method is for rapid processing.

(Evaluation of Color Reproducibility) From the obtained characteristic curve, the ratio of the yellow (B) density and the cyan (R) density at an exposure amount of 0.5 CMS was determined. The concentration ratio (R / B)
Is closer to 0.7, it means that the image forming method is excellent in color reproducibility (color balance).

(Evaluation of image storability) The B density (Dmin (B0)) of the unexposed area immediately after the treatment was determined, stored for one day under the condition of constant temperature and humidity of 65 ° C.-70%, and then again exposed area. B concentration (Dmin (B1)) of was determined. Image storability was evaluated by determining the increase in B density as follows. B density increase: Dmin (B1) -Dmin (B0) The smaller the increase in color, the better the image storability is. The obtained results are shown in Tables 4-6.

[0185]

[Table 4]

[0186]

[Table 5]

[0187]

[Table 6]

[0188]

Embedded image

From the results of Tables 4 to 6, the following can be seen. Experiment A02, A03, A08, A09, A14, A
18 and A28, when color development processing is carried out using a developing agent as described in JP-A-4-45440, Dmin remarkably increases and S _0.2 (R) becomes too small to be measured. growing.

From Experiments A01 and A04 to 06, the comparative developing agent ExD-1, which is widely used for color developing processing of color negative films, was subjected to color developing processing using the developing agent of the present invention. Becomes smaller, and B
The density increase is large. However, experiments A07-A4
As is clear from No. 8, when the yellow coupler of the present invention is used, even if color development processing is performed using ExD-1, S
_While no significant improvement was observed in _0.2 (R), (R / B) density ratio, and B density enhancement, when color development processing was performed using the developing agent of the present invention, S _0.2 (R), (R / B) concentration ratio,
It can be seen that the increase in B density is significantly improved.

Table 7 shows ExD-1 and D- as developing agents.
The experimental results when 18 is selected are shown. PKa in the table is the pKa value of the yellow coupler.

[0192]

[Table 7]

From Table 7, S by the image forming method of the present invention
_It can be seen that both _0.2 (R), (R / B) density ratio and B density are significantly improved, and that the pKa of the yellow coupler is preferably 6.5 or more, more preferably 7.0 or more.

Since the color developing agent of the present invention is likely to form an ion pair salt with a yellow coupler, it is presumed that the diffusion to the lower layer is slow, and the yellow coupler of the present invention suppresses the formation of an ion pair salt to remarkably form a color. It is considered that the diffusion of the developing agent became faster.

Example 2 The same treatment as in Example 1 was carried out as follows.

Treatment process (Process) (Treatment time) (Treatment temperature) (Replenishment amount) (Tank capacity) Color development 60 seconds 45.0 ℃ 140 ml / m ² 2.0 liter Bleach fixing 60 seconds 45.0 ℃ 120 ml / m ² 2.0 liter Water wash (1) 15 seconds 45.0 ℃ − 0.5 liters Washed with water (2) 15 seconds 45.0 ℃ − 0.5 liters Washed with water (3) 15 seconds 45.0 ℃ 120ml / m ² 0.5 liters Stabilized 2 seconds Room temperature Apply dry 20 seconds 85 ℃ The crossover time from color development to bleach-fixing and from bleach-fixing to water washing (1) is 5 seconds. The average amount of processing solution taken out per 1 m ^{2 of the} light-sensitive material is 40 ml. Washing (1) to (3) is a countercurrent multistage cascade method. Washing with water (1) to (3) was carried out by a multi-chamber washing method in which the wiper blade was able to move in the liquid without crossover in the air. Total processing time is 2 minutes 47
Seconds. Further, as evaporation correction in each tank, JP-A-3-28
As described in No. 0042, the temperature and humidity of the outside air of the processor were detected by a thermohygrometer, and the evaporation amount was converted and corrected. Ion-exchanged water for washing water was used as the water for evaporation correction.

The composition of the treatment liquid used in each step is shown below. (Color developer) Mother liquor Replenisher Diethylenetriaminepentaacetic acid 4.0 g 4.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 g 3.0 g Potassium hydroxide 10.0 g 15.0 g Potassium iodide 1.3 g 0 g Potassium bromide 4.2 g 0 g Potassium carbonate 50.0 g 50.0 g Sodium sulfite 4.0 g 6.8 g Hydroxylamine 35 mmol 50 mmol Color developing agent (ExD-1) 30 mmol 40 mmol Water was added 1000 ml 1000 ml pH 10.10 11.80

(Bleach-fixing solution) mother liquor replenishing solution bleaching agent (ferric ammonium salt of compound A) 0.15 mol 0.20 mol ethylenediaminetetraacetic acid ferric ammonium dihydrate 0.05 mol 0.07 mol sulfinic acid (compound B) 0.1 mol 0.15 mol Fixing accelerator (Compound C) 0.3 mol 0.4 mol Ammonium thiosulfate (75%) 300 ml 400 ml Ammonium sulfite 30 g 45 g Succinic acid 30 g 40 g Water 1000 ml 1000 ml pH

[0199]

Embedded image

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stable liquid) Mother liquor and tank liquid are common Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 g Ethylenediaminetetraacetic acid disodium salt 0.05 g Add water to 1000 ml pH 8.0

The bleach-fix solution was subjected to in-line silver recovery with a silver recovery device. The silver recovery device is a small electrolytic silver recovery device with an anode of carbon and a cathode of stainless steel drum.
A current density of 0.5 A / dm ² was used. In the above processing steps, continuous processing was carried out until the replenishing amount of the bleach-fixing solution became 3 times the tank capacity. Further, the developing agent in the color developing solution was replaced with the developing agent of the present invention in an equimolar amount, the same treatment was carried out, and the lower layer developing property, color reproducibility and image storability were evaluated in the same manner as in Example 1.

As a result, as in the case of Example 1, the image forming method of the present invention provided an image excellent in developability, color reproducibility and image storability of the lower layer.

Further, the processing time for color development is 30 seconds, 4
When processed in the same manner except that it was changed to 5 seconds, 60 seconds, 75 seconds, 90 seconds, 120 seconds and 180 seconds, the deterioration of the developability of the lower layer was significantly large in the comparative yellow coupler in a short time of 90 seconds or less. However, it was significantly improved by the yellow coupler of the present invention.

Example 3 1) Support The support used in this example was prepared by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin p.326 as an ultraviolet absorber.
After drying 2 parts by weight (manufactured by Geigy) by a conventional method,
After melting at 300 ° C, extruded from a T-die and longitudinally stretched 3.0 times at 140 ° C, then laterally stretched 3.0 times at 130 ° C, and further heat set at 250 ° C for 6 seconds. A PEN film having a thickness of 90 μ was obtained. In addition, a part of it is wrapped around a stainless steel core with a diameter of 20 cm,
A thermal history of 8 hours was given. 2) Coating of undercoat layer The above-mentioned support is subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides thereof,
An undercoat liquid having the following composition was applied to each surface to form an undercoat layer on the high temperature surface side during stretching. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. was used.
cm width supports are treated at 20 m / min. At this time, the current
From the voltage reading, the object to be processed is 0.375KV ・ A ・
Min / m ² was processed. The discharge frequency during the treatment was 9.
At 6 KHz, the gap clearance between the electrode and the dielectric roll was 1.6 mm. The UV discharge treatment was performed while heating at 75 ° C. Further, the glow discharge treatment was performed by irradiating with a cylindrical electrode of 3000 W for 30 seconds. Gelatin 3 g Distilled water 25 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g p-Chlorophenol 0.5 g Resorcin 0.5 g Cresol 0.5 g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g trimethylolpropane triazine 0.2 g trimethylolpropane tristoluene diisocyanate 0.2 g methanol 15 cc acetone 85 cc formaldehyde 0.01 g acetic acid 0.01 g Concentrated hydrochloric acid 0.01g

3) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer and a sliding layer were provided as back layers on one surface of the support after undercoating. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution became 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water, and sprayed in a baking furnace heated to 650 ° C. to obtain a bluish average particle diameter of 0.0
A fine powder of tin oxide-antimony oxide composite having a size of 05 μm was obtained. The specific resistance of this fine particle powder was 5 Ω · cm. A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, roughly dispersed by a stirrer, and then retained in a horizontal sand mill (trade name: Dynomill; WILLYA. BACHOFENAG) until the residence time was 30 minutes. It was dispersed and prepared. At this time, the average particle size of the secondary aggregate was about 0.04 μm.

3-1-2) Coating of conductive layer The following formulation was applied so that the dry film thickness would be 0.2 μm,
It was dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight p-Chlorophenol 0.5 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight The resistance of the obtained conductive film was 10 ^8.0 (100 V), and it had an excellent antistatic property. 3-2) Coating of magnetic recording layer Magnetic substance Co-deposited γ-Fe ₂ O ₃ (long axis 0.14 μm, single axis 0.
Needle-shaped 03μm, specific surface area 41m ² / g, saturation magnetization 89em
u / g, the surface is treated with 2% by weight of Fe ₂ O ₃ with aluminum oxide and silicon oxide respectively, coercive force 930 Oe, Fe ⁺²
/ Fe ⁺³ ratio was 6/94) 1100 g was added with water 220 g and poly (polymerization degree 16) oxyethylenepropyltrimethoxysilane silane coupling agent 150 g, and well kneaded for 3 hours in an open kneader. The roughly dispersed viscous liquid was dried at 70 ° C. for one day to remove water.
The surface was treated by heating at 0 ° C. for 1 hour to prepare surface-treated magnetic particles. Further, the following formulation was used, and the mixture was kneaded again in an open kneader.

The surface-treated magnetic particles 1000 g Diacetylcellulose 17 g Methylethylketone 100 g Cyclohexanone 100 g Further, 200 with a sand mill (1/4 G) with the following formulation.
Finely dispersed at rpm for 4 hours. The above kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g Further diacetyl cellulose and C ₂ H ₅ C (CH
20 wt% of ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ with respect to the binder
Was added. The obtained liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity was about 80 cp. The coating was carried out on the above conductive layer with a bar coater, and the film thickness was 1.2 μm. Amount of magnetic material 0.6g /
It was applied as a m ^2. Silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as an abrasive
Were added so that the respective amounts would be 10 mg / m ² . Dry 1
It was carried out at 15 ° C for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C). When using a blue filter in Status M of X- write, increment of the color density of D ^B of the magnetic recording layer was about 0.1. The saturation magnetization moment of the magnetic recording layer was 4.2 emu / m ² , the coercive force was 923 Oe, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer The following prescription liquid was applied so that the coating amount of the solid content of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ compound a 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H compound b 9 mg / m ² Compound a / compound b (6: 9) was xylene and propylene glycol monomethyl ether (volume ratio 1:
1) was heated and dissolved in the same amount of liquid at 105 ° C., and this liquid was poured into 10 times amount of propylene glycol monomethyl ether (25 ° C.) to obtain a fine dispersion liquid. Furthermore, dilute in 5 times the amount of acetone and re-disperse with a high pressure homogenizer (200 atm) to obtain a dispersion (average particle diameter 0.01 μ).
It was added and used. The performance of the obtained sliding layer is
Dynamic friction coefficient 0.06 (5mmφ stainless steel ball, load 1
00g, speed 6cm / minute), coefficient of static friction 0.07
(Clip method) and has excellent characteristics. The sliding property with respect to the emulsion surface, which will be described later, was also the dynamic friction coefficient of 0.12.

4) Coating of light-sensitive material layer Next, each layer having the same photosensitive layer composition as in Example 1 was multilayer-coated on the side opposite to the back layer obtained above to prepare a color negative photographic film. When the obtained color negative film was treated in exactly the same manner as in Example 1 and Example 2,
By the image forming method of the present invention, an image excellent in color reproducibility and image storability was obtained.

Example 4 Sample 20 of Example 2 described in JP-A-5-204109
Sample 401 was prepared in exactly the same way as in Example 1, and sample 40
1st, 11th and 12th layer yellow couplers (ExY-3,
Sample 402 was prepared in exactly the same manner except that ExY-2) described in this patent was changed to the yellow coupler (Y-10) of the present invention in an equimolar amount. Example 1 for two samples
In the same manner as described above, processing was performed using the developing agents ExD-1 and D-18, and the color reproducibility and the image storability were evaluated.
As a result, even in a light-sensitive material containing a donor layer having a multi-layer effect on the red-sensitive layer like Samples 401 and 402, an image excellent in color reproducibility and image storability was obtained by the image forming method of the present invention.

Example 5 Sample 101 of Example 1 described in JP-A-4-147133.
In the above, the coupler (C-6) in the 16th and 17th layers is replaced by the coupler (C-5: yellow coupler Y-11 of the present invention).
Sample 501 was prepared in exactly the same manner except that the equimolar amount was changed. Furthermore, a sample 502 was prepared in exactly the same manner except that the coupler (C-5) in the fifteenth to seventeenth layers of the sample 501 was changed to an equimolar amount with the comparative coupler (ExY-2). Samples 501 and 502 were treated in exactly the same way as in Example 1 of the patent. Further, Samples 501 and 502 were N-ethyl- in the color developer of Example 1 of the patent.
(Β-Methanesulfonamidoethyl) -3-methyl-4
-Aminoaniline sulfate is used as the developing agent of the present invention (D-1
Processing was carried out in exactly the same manner except that the equimolar amount was changed to 8) and the color development time was changed to 1 minute.

After the processing, the color reproducibility and the image storability were evaluated in the same manner as in Example 1. As a result, an image excellent in color reproducibility and image storability was rapidly obtained by the image forming method of the present invention. .

[0215]

According to the present invention, the color reproducibility and the image storability are excellent even after the rapid processing.

Claims (2)

[Claims] 1. A hydrophilic colloid layer of at least one layer provided on a support, which is represented by the following general formula (I) and has a pKa at a coupling active position of 6.2 or more and 11.0 or more.
A silver halide color photographic light-sensitive material containing at least one of the following yellow couplers is color-developed in the presence of at least one tetrahydroquinoline-based color developing agent represented by the following general formula (D). Color image forming method. General formula (I) [In the above formula (I), R _a represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, or a di-substituted amino group, and R _b represents a halogen atom, an alkoxy group, a cyclo group. It represents an alkoxy group, an aryloxy group, an alkyl group, or a dialkylamino group, R _c represents a group which can be substituted on the benzene ring, and X represents a group which can be released by a coupling reaction with an oxidized product of a developing agent. , N represents an integer of 0 to 3. General formula (D) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each combination of R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ , at least one set is a substituent. R ₇ and R ₈ each represent a substituent.
m represents an integer of 0 to 3. 2. The color image forming method according to claim 1, wherein the color developing time is 25 seconds or more and 90 seconds or less.