JPH1062928A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for processing the silver halide color photographic sensitive material having a high silver chloride content and rapid processing aptitude and superior in stability with the lapse of time and sensitivity and good in gradation. SOLUTION: This silver halide color photographic sensitive material has blue-, green-, and red-sensitive layers and non-photosensitive layers and at least one of the photosensitive layers contains flat silver halide grains occupying >=50% of the projection areas of the total silver halide grains and having an aspect ratio of >=2 and a silver chloride content of >=60mol%, and this photosensitive material is color developed with a processing solution containing a tetrahydroquinoline type color developing agent represented by the formula in which each of R1 -R6 is an H atom or a substituent but at least one of the couples of R1 and R2 , R3 and R4 , and R5 and R6 is both a substituent; R7 is an alkyl or aryl or heterocyclic group; R8 is a substituent; and (m) is an integer of 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material which is excellent in rapid processing, gives high sensitivity and good gradation, and has excellent stability over time.

2. Description of the Related Art It is well known that tabular grains are suitable as grains of a photosensitive photographic emulsion in terms of sensitivity, color sensitization efficiency, image quality of graininess and sharpness, and the like. As the tabular silver halide grains, tabular grains having twin planes and having a principal plane of {111} planes and a principal plane of {100}
There are tabular grains composed of planes.

In response to recent demands for speeding up and simplifying development processing, the use of silver halide grains having a high content of silver chloride, which has high solubility even in silver halide, has been required. Is more advantageous than Main surface is $ 11 with high silver chloride content
The tabular grains having a 1｝ plane are described in, for example, US Pat. Nos. 4,983,508 and 5,185,239. For tabular grains containing high silver chloride and having a principal plane consisting of {100} planes, see, for example, European Patent No. 534,3.
No. 95A, U.S. Pat. Nos. 5,264,357, 5,
No. 275,930.

[0003] Silver chloride emulsions are generally known to have rapid developability. Each silver halide grain has a long induction period until the start of development, but is once reduced to metallic silver once reduction by the developing agent starts. Therefore, it is easy to show characteristics with low sensitivity and high gamma. Such characteristics are suitable for printing materials, but photographic materials such as color negative films require high sensitivity, low gamma and long latitude. If the development time is very short, a low gamma and a long latitude can be achieved, but the sensitivity is significantly reduced. A method for solving such a problem is disclosed in U.S. Pat. No. 5,491,050. That is, this is a method in which development is performed using a color developing solution containing a p-phenylenediamine color developing agent in the presence of a 1-phenylpyrazolidin-3-one compound. However, since the amount of the 1-phenylpyrazolidin-3-one-based compound is very small and greatly affects the developability, it has been found that the photographic performance greatly varies with the aging of the processing solution.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide emulsion having rapid developability of a silver chloride emulsion, excellent stability over time, high sensitivity and good gradation. It is to provide a method of processing the material.

The above object of the present invention is achieved by the following method. That is, the support has at least one blue-sensitive layer, a green-sensitive layer, a red-sensitive layer, and a non-photosensitive layer, and at least one of the photosensitive layers has an aspect ratio of at least one. The sum of the projected areas of the tabular silver halide grains of 2 or more is 5 times the total projected area of the silver halide grains.
A silver halide photographic light-sensitive material containing a photosensitive silver halide occupying 0% or more and having a silver chloride content of 60 to 100 mol% is subjected to tetrahydroquinoline-based color development represented by the following general formula (D). A method for processing a silver halide color photographic light-sensitive material, wherein color development processing is performed using a processing solution containing at least one principal agent.

Embedded image 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 pair is a substituent. R ₇ represents an alkyl group, an aryl group or a heterocyclic group. R ₈ represents a substituent. m is 0
Represents an integer from to 3.

In the present invention, the compound represented by the general formula (D)
The compound to be prepared will be described in detail. First, the general formula (D)
R in the compound represented by₁ , R_Two , R_Three , R_Four , R
_Five , R ₆ , R₇ , R₈ And m in detail
You. R₁ , R_Two , R_Three And R_Four Are the same but different
And each represents a hydrogen atom or a substituent. Learn more
Is R₁ , R_Two , R_Three And R_Four Is a hydrogen atom or a substituent
Yes, examples of the substituent include a halogen atom, an alkyl group,
Aryl group, heterocyclic group, cyano group, nitro group, hydro
Xyl group, carboxyl group, sulfo group, alkoxy group,
Aryloxy, acylamino, amino, alkyl
Ruamino group, anilino group, ureido group, sulfamoyl
Amino group, alkylthio group, arylthio group, alkoxy
Cicarbonylamino group, sulfonamide group, carbamoy
Group, sulfamoyl group, sulfonyl group, alkoxyca
Rubonyl group, heterocyclic oxy group, azo group, acyloxy
Group, carbamoyloxy group, silyl group, silyloxy
Group, aryloxycarbonylamino group, imide group,
Telocyclic thio group, sulfinyl group, phosphonyl group, aryl
A luoxycarbonyl group and an acyl group. These are al
Kill, alkenyl, alkynyl, aryl,
Droxyl, nitro, cyano, halogen or
Is other oxygen, nitrogen, sulfur or carbon
It may be substituted with a substituent formed by an atom.

Examples of the substituents of R ₁ , R ₂ , R ₃ and R ₄ will be described in more detail. Examples of the halogen atom include a fluorine atom and a chlorine atom. The alkyl group has 1 to 2 carbon atoms.
5, preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2- Methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, hydroxymethyl, 2-carboxylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2, 3-dihydroxypropyl, 3,4-dihydroxybutyl, methanesulfonamidomethyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobuty , 4-carbamoyl-butyl, 2
-Carbamoyl 1-methylethyl, carbamoylaminomethyl, 4-nitrobutyl, 2- (2-hydroxyethoxy) ethyl, 2- [2- (2-hydroxyethoxy)
Ethoxy] ethyl, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl, 2- [2-
(2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethyl, 2- (2-methoxyethoxy) ethyl, 2- [2- (2-methoxyethoxy) ethoxy] ethyl, 2- (2- [2- (2-methoxyethoxy) ethoxy] ethoxy) ethyl, 2- [2- (2-
[2- (2-methoxyethoxy) ethoxy] ethoxy)
Ethoxy] ethyl, 2- (2-ethoxyethoxy) ethyl and 2- [2- (2-butoxyethoxy) ethoxy] ethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, such as phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the kind of element 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, such as methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, for example, phenoxy, p-methoxyphenoxy, m- (3
-Hydroxypropionamido) phenoxy. The acylamino group is an acylamino group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms.
-Methoxypropionamide, p-nitrobenzoylamide. The 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. The anilino group has 6 to 2 carbon atoms.
Examples of the anilino group 4 include anilino, m-nitroanilino, and N-methylanilino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as ureide, methyl ureide, N, N-diethyl ureide and 2-methanesulfonamidoethyl ureide.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably 0 to 6 carbon atoms, for example, dimethylsulfamoylamino, methylsulfamoylamino, 2-methoxyethylsulfamoylamino. The alkylthio group has 1 to 1 carbon atoms.
16, preferably an alkylthio group having 1 to 6 carbon atoms, for example, methylthio, ethylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 24 carbon atoms, such as 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, such as 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, such as 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. The sulfonyl group has 1 carbon atom
To 16, preferably an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, such as methanesulfonyl, ethanesulfonyl and 2-chloroethanesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl. The heterocyclic oxy group has 1 to 1 carbon atoms.
5 is a 5- or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one oxygen, nitrogen or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element are one. However, the number may be plural, such as 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.
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, such as 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,
t-butyldimethylsilyl. The silyloxy group is a silyloxy group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, such as phenoxycarbonylamino, 4-cyanophenoxycarbonylamino, and 2,6-dimethoxyphenoxycarbonylamino. The imide group has 4 to 1 carbon atoms
The imide group 6 is, for example, N-succinimide or N-phthalimide. The 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, having at least one heteroatom and one kind of element constituting the ring. It may be plural, for example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfinyl group has 1 to 16 carbon atoms,
Preferably it is a C1-C6 sulfinyl group, for example, 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, such as phenoxycarbonyl, 2-methylphenoxycarbonyl, and 4-acetamidophenoxycarbonyl. As the acyl group, an acyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetyl, benzoyl,
4-chlorobenzoyl.

R ₅ and R ₆ each represent a hydrogen atom or a substituent. In this case, the substituent represents an alkyl group, an aryl group or a heterocyclic group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . However, R ₅ , R ₆
Is a heterocyclic group, it is bonded to a carbon atom constituting the heterocyclic ring of the heterocyclic group. R ₇ represents an alkyl group, an aryl group or a heterocyclic group. For details, see R ₁ ,
It has the same meaning as that described for R ₂ , R ₃ and R ₄ . However, when R ₇ is an alkyl group, among the carbon atoms in R ₇ , the carbon atom directly bonded to the nitrogen atom in the general formula (D) includes a hydrogen atom and a carbon atom other than the two elements. Are not combined. When R ₇ is a heterocyclic group, the nitrogen atom in the general formula (D) to which R ₇ is bonded is connected to a carbon atom constituting the hetero ring of the heterocyclic group. R ₈ represents a substituent. For details, see R ₁ , R ₂ , R
₃ and is synonymous to those described in R _4. m represents an integer of 0 to 3.

Among the compounds represented by the general formula (D),
Compounds represented by the following formulas (DD-1) and (DD-2) are particularly preferred.

[0013]

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Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R
₁₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each of R ₁₁ and R _12, R ₁₃ and R _14, R ₁₅ and R _16, which is at least one of both substituents. R ₁₇ represents an alkyl group, an aryl group or a heterocyclic group. R ₉ represents a hydrogen atom or a substituent.

Embedded image In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each of R ₂₁ and R _22, R ₂₃ and R _24, R ₂₅ and R _26, at least one of which is both substituents. R ₉ and R ₂₈ represent a hydrogen atom or a substituent, and n represents an integer of 2 to 5.

In the general formula (DD-1), R ₁₁ , R ₁₂ ,
Preferred combinations of R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ will be described below. R ₁₈ is a hydrogen atom, an alkyl group or an alkoxy group, R ₁₇ is an alkyl group, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Is preferably a combination each of which is a hydrogen atom or an alkyl group. Here, the alkyl group and the alkoxy group include those substituted with another substituent. In this combination,
More preferably, at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ 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, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group is preferable. Particularly, it is preferably an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group.

As a more preferred combination, R ₁₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or
And R ₁₇ is an alkyl group having 1 to 6 carbon atoms, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this combination, it is more preferable that at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ 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, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group. It is particularly preferable that the alkyl group is substituted with a hydroxyl group, a carboxyl group, a ureido group or a sulfonamide group.

A more preferred combination is R₁₈Is
An alkyl group having 1 to 6 carbon atoms;₁₇Has 1 to 6 carbon atoms
Is an alkyl group of₁₁, R₁₂, R₁₃, R₁₄, R_FifteenPassing
And R ₁₆Each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
Is preferred. This combination smells
R₁₁, R₁₂, R₁₃, R₁₄, R_Fifteen, R₁₆, R₁₇And R₁₈
Alkyl at least one of which is substituted with a water-soluble group
Group, more preferably a hydroxyl group,
Ruboxyl group, sulfo group, alkoxy group, acylamino
Group, amino group, alkylamino group, ureido group, sulf
Amoylamino group, sulfonamide group, carbamoyl
Group, a sulfamoyl group, or a sulfonyl group
Preferably an alkyl group, especially hydroxyl
Group, carboxyl group, ureido group, sulfonamide group
It is preferably a substituted alkyl group.

In a more preferred combination, R ₁₈ is a methyl group or an isopropyl group, and R ₁₇ has 1 carbon atom.
And R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
_{A combination in which 15} and R ₁₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In this combination, it is more preferable that at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ 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, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group is preferable. Particularly, it is preferably an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group.

R in the general formula (DD-2)_{twenty one}, R_{twenty two},
R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₆, R₉And R ₂₈About below
The preferred combinations are described below. R₂₈Is hydrogen
An atom, an alkyl group or an alkoxy group,₉Is water
A hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}, R_{twenty five}And R₂₆Is water
Combinations which are an atom or an alkyl group are preferred. here
Alkyl, alkoxy, aryl and hetero
Ring groups include those substituted with other substituents. Replace
Groups include hydroxyl, carboxyl, sulfo
Group, alkoxy group, acylamino group, amino group, alkyl
Ruamino group, ureido group, sulfamoylamino group,
Sulfonamide, carbamoyl, sulfamoyl, etc.
Or a sulfonyl group, particularly a hydroxyl group,
Ruboxyl, ureido and sulfonamide groups are preferred
No.

As a more preferable combination, R ₂₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom having 1 to 6 carbon atoms.
R ₉ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ Is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Here, the alkyl group, the alkoxy group and the aryl group include those substituted with another substituent. As the substituent, a hydroxyl group, 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 is preferable. Particularly, a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are preferred.

More preferably, R ₂₈ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂₁ and R _{21 are the same} .
_It is preferable that each of ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Here, the alkyl group includes those substituted with another substituent. As the substituent, a hydroxyl group, 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 is preferable. Particularly, a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are preferred.

In a more preferred combination, R ₂₈ is a methyl group or an isopropyl group, R ₉ is a hydrogen atom or a methyl group, and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are Combinations of a hydrogen atom or an alkyl group having 1 to 3 carbon atoms are preferred. Here, the alkyl group includes those substituted with another substituent. As the substituent, a hydroxyl group, 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 is preferable. Particularly, a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are preferred.

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

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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The compound represented by the general formula (D) is very unstable when stored as a free amine,
In general, it is preferable to produce and store the salt as a salt of an inorganic acid or an organic acid, and then to form a free amine for the first time when the salt is added to the treatment solution. Examples of the inorganic and organic acids that form a salt of the compound of the formula (D) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-
1,5-disulfonic acid and the like can be mentioned. Among these, a salt of sulfuric acid or p-toluenesulfonic acid is preferable, and salt formation as a salt with sulfuric acid is most preferable. The color developing agent used in the present invention is, for example, a journal,
73 of the American Chemical Society,
It can be easily synthesized according to the method described on page 3100 (1951). Compound (D-30), (D-1
8), (D-32), (D-37) and (D-39) can be synthesized by the method described in JP-A-7-287370.

The color developing agent used in the present invention can be used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compounds to be combined are shown below, but are not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 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

As the compound to be combined, P-3 and P-phenylenediamine are particularly preferable among the above-mentioned p-phenylenediamine derivatives.
5, P-6 or P-10. In addition, these p
-Phenylenediamine derivative and sulfate, hydrochloride, sulfite, p-toluenesulfonate, nitrate, naphthalene-
It is generally used in salts such as the 1,5-disulfonate. In the present invention, the treatment composition may be in a liquid state or a solid state (for example, a powdery state or a granular state). These compounds can be used in combination of two or more depending on the purpose. The amount of the aromatic primary amine developing agent to be used is preferably from 0.001 mol to 1 liter of the color developer.
0.2 mol, more preferably 0.005 mol to 0.1
Is a mole.

In the color developer used in the present invention, compounds which directly preserve the aromatic primary amine color developing agent are disclosed in JP-A-63-5341 and JP-A-63-106.
655 or various hydroxylamines described in JP-A-4-144446, hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, 63-44657.
And phenols described in JP-A-63-58443, α-hydroxyketones and α-aminoketones described in JP-A-63-44656, and various sugars described in JP-A-63-36244. Also, in combination with the above compounds, JP-A-63-4235 and JP-A-63-2425
No. 4, No. 63-21647, No. 63-146040
Monoamines described in JP-A Nos. 63-27841 and 63-25654;
Diamines described in 3-14640 and 63-43139, 63-21647 and 63-26655
And polyamines described in JP-A-63-44655,
The nitroxy radicals described in JP-A-63-53551,
Alcohols described in JP-A-63-43140 and JP-A-63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239947 can be used. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749; salicylic acids described in JP-A-59-180588; alkanolamines described in JP-A-54-3582; Polyethylene imines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained as necessary. In particular, when hydroxylamines are used, the above-mentioned alkanolamines and aromatic polyhydroxy compounds are preferably used in combination. Particularly preferred preservatives are hydroxylamines represented by the general formula (I) in JP-A-3-144446. Among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferred. The addition amount of these preservatives is 20 to 200 mmol, preferably 30 to 150 mmol, per liter of the color developer.

In addition, various additives described in JP-A-3-144446 can be used in the color developer used in the present invention. For example, carbonic acids, phosphoric acids, boric acids, hydroxybenzoic acids, etc. described in page (9) of the same patent can be used as a buffer for maintaining pH. The color developer is adjusted to pH 9.0 to 12.5 using these buffers.
Is preferably maintained. More preferably, 9.5 to 1
1.5. Examples of the antifoggant include halide ions and organic antifoggants described on page (10). In particular, when the concentration of the developing agent in the color developer is as high as 20 mmol / L or more, or when high-temperature processing at 40 ° C. or more is performed, the bromide ion concentration is preferably somewhat high, and more preferably from 17 mmol / L to 60 mmol. . If necessary, halogen can be removed using an ion-exchange resin or an ion-exchange membrane to control the concentration in a preferable range. As the 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 represented by N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be used. Preferred chelating agents include compounds having biodegradability. An example of this is disclosed in JP-A-63-146998.
JP-A-63-199295, JP-A-63-267
750, JP-A-63-267751, JP-A 2-2
29146, JP-A-3-186841, German Patent 3
739610, European Patent 468325 and the like. Further, 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 replenishment amount of the color developer used in the present invention is preferably 550 ml or less, more preferably 450 ml or less, and more preferably 400 ml / m ^{2 in} the case of a photosensitive material for photography.
Hereinafter, 80 ml or more is most preferable. By reducing or not including the bromide ion concentration in the replenisher,
It can be 300 ml or less. The processing temperature of the color developer is preferably 35 ° C or higher, more preferably 40 ° C or higher and 50 ° C or lower. The processing time of the color developer is preferably 3 minutes and 15 seconds or less, more preferably 30 seconds to 2 minutes and 30 seconds. It is preferable to prevent evaporation of the liquid and air oxidation. The contact area between the photographic processing solution 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 )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, more preferably Preferably it is 0.0005-0.01.
As a method of 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,
A slit developing method described in JP-A-63-216050 can be exemplified. Further, it is preferable that the processing solution in the replenishment tank of the color developer or the processing layer is shielded with a high boiling point organic solvent or a high molecular compound to reduce the contact area with air. Particularly, liquid paraffin, organosiloxane and the like are preferable. Reducing the aperture ratio can be applied not only to both color development and black-and-white development, but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. 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 activity of the developing solution is increased by adding a processing chemical called a regenerating agent, and used again as a processing solution. . In this case, the regeneration rate (the percentage of overflow in the replenisher)
It is preferably at least 50%, particularly preferably at least 70%. 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 of 1986) issued by Mitsubishi Kasei Kogyo. Among the anion exchange resins, JP-A-2-952 and JP-A-1-28115
The resin having the composition described in No. 2 is preferred.

In the present invention, the color-developed photosensitive material is subjected to a desilvering process. The desilvering process referred to here basically comprises a bleaching process and a fixing process, but is constituted by a bleach-fixing process in which these processes are performed simultaneously and a combination of these processes. Examples of the bleaching agent include the above-mentioned JP-A-3-14444.
As described on page 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-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid are mentioned. In addition, complex salts such as citric acid, tartaric acid and malic acid can be used as bleaching agents. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex salt are particularly preferable. These iron (III) aminopolycarboxylic acid complex salts are particularly useful in a bleaching solution and a bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
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;
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40943, JP-A-49-59644 and JP-A-53-96444
No. 94927, No. 54-35727, No. 55-265
Nos. 06 and 58-163940; bromide ions and the like. Among them, a compound having a mercapto group or a disulfide group is 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.
Are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. 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 used in the present invention, in addition to the bleaching agent, a rehalogenating agent, a pH buffering agent and known additives described in JP-A-3-144446 (page 12) can be used. In the bleaching solution and the bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are acid dissociation constants (pk
a) is a compound of 2 to 6, specifically, acetic acid, propionic acid, hydroxyacetic acid succinic acid, maleic acid, glutaric acid, fumaric acid, malonic acid, adipic acid, etc., and particularly preferably succinic acid , Maleic acid and glutaric acid. The pH of the bleaching solution or bleach-fixing solution is usually 4.0 to 4.0.
8.0, but lower p for faster processing
H can also be processed.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides. Use is common, especially ammonium thiosulfate being the most widely used. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or 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 Diaminetetraacetic acid, 1,2
-Propylenediaminetetraacetic acid. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferred. The fixer and the bleach-fixer have a pKa of 6. for pH adjustment.
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 / l. The imidazole compound represents imidazole and its derivatives, 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.
Further, the alkyl group, alkenyl group, and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom, or the like. The preferred total carbon number of the substituents of imidazole is 1 to 6, and the most preferred substituent is a methyl group.

Hereinafter, specific examples of the imidazole compound will be described, 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, 4-methyl-imidazole,
The most preferred compound is imidazole.

When the replenishment system is employed in the processing of the present invention, the replenishment amount of the fixing solution or the bleach-fixing solution is preferably from 100 to 3000 ml per 1 m ² of the light-sensitive material, and more preferably from 300 to 1800 ml. Replenishment of the bleach-fixing solution may be carried out as a bleach-fixing replenisher, or by using an overflow solution of the bleaching solution and the fixing solution as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389. You may. In the present invention, the total processing time of the desilvering step comprising a combination of bleaching, bleach-fixing and fixing is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The processing temperature is 30 to 60 ° C, preferably 35 to 60 ° C.
55 ° C.

The processing solution having a bleaching ability used in the present invention is particularly preferably subjected to aeration during processing, since photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak's Z-121, Using Process C-
41, Third Edition (1982), pages BL-1 to BL-2. 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 processing is carried out as described in JP-A-3-33847, page 8, upper right column, line 6 The contents described in the second row from the lower left column can be used as they are.

The processing solution having a fixing ability used in 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 the silver recovery method, an electrolysis method (French Patent No. 2,299,667) is used.
), A precipitation method (described in JP-A-52-73037, German Patent No. 2,331,220), and an ion-exchange method (JP-A-51-17114, German Patent No. 2,548,237).
No. 1) and a metal substitution method (UK Patent No. 1,353,80)
No. 5) is effective. These silver recovery methods are preferably performed in-line from the tank liquid, because the rapid processing suitability is further improved. Further, the processing solution having bleaching ability used in the present invention can be reused after collecting the overflow solution used for the processing, correcting the composition by adding components, and then reusing it. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. With respect to the details of the reproduction, the matters described in Fujifilm Processing Manual, Fujicolor Negative Film, CN-16 processing (revised in August 1990), pages 39 to 40, issued by Fuji Photo Film Co., Ltd. can be applied. The kit for adjusting the processing solution having the bleaching ability used in the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied in the form of a powder and have low hygroscopicity. Makes it easier to make powder.
From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added 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 halide photography-" (edited by the Photographic Society of Japan, published by Corona, 1979)
Year) can be used. Specifically, in addition to electric field regeneration, a method for regenerating a bleaching solution with bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, etc. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm to regenerate. And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. Others
It is also preferable to remove the 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 specific method for enhancing the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a light-sensitive material, and a method described in JP-A-62-183460.
No. 2-183461, a method of increasing the stirring effect by using the rotating means, and further, by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and causing the emulsion surface to become turbulent, thereby further stirring. A method for improving the effect and a method for increasing the circulating flow rate of the entire processing liquid can be given. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the 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 increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator. The automatic developing machine used in the present invention is disclosed in JP-A-60-191257, JP-A-60-191258,
It is preferable to have a photosensitive material conveying means described in JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. 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 the fixing ability, usually,
A water washing process is performed. After processing with a processing solution having fixing ability,
A simple treatment method of performing a stabilization treatment using a stabilizing solution without substantially performing water washing can also be used. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the
Society of Motion Pictureand Television Engineers
Vol. 64, pp. 248-253 (May, 1955). The number of stages is preferably 2 to 4 stages. The replenishing amount is 1 to 50 times, preferably 1 to 30 times, more preferably 1 to 50 times the amount brought in from the previous bath per unit area.
It is 10 times. As a method of efficiently reducing the replenishment amount, a so-called multi-chamber washing method in which a washing tank or a stabilizing bath is divided by a partition wall, and the photosensitive material is processed in a liquid without passing through a slit portion of a wiper blade or the like to enter the air. Alternatively, a stable treatment is preferably used.

According to the above-mentioned multi-stage countercurrent method or multi-room water washing method, the amount of washing water can be greatly reduced. Problems such as adhesion to materials occur. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, JP
No. -8,542, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986) Sankyo Publishing Co., Ltd. "Sterilization, Sterilization, and Mold Prevention Techniques of Microorganisms" edited by the Sanitation Technology Society (1982), Japan Society of Industrial Technology, "The Encyclopedia of Bactericidal and Antifungal Agents" (ed. 1986)
Can be used.

The pH of the washing water and the stabilizing solution in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The temperature and time can also be variously set depending on the characteristics of the photosensitive material, the application, etc., but generally ranges from 15 to 45 ° C. for 20 seconds to 10 minutes, preferably from 25 to 40 ° C. for 30 seconds to 5 minutes. Selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, JP-A-57-8543, JP-A-58-14834, and JP-A-60-2
All known methods described in 20345 can be used.

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

Various surfactants can be contained in the washing water and the stabilizing solution in order to prevent unevenness of water droplets when the processed photosensitive material is dried. Among them, a nonionic surfactant is preferably used, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

It is preferable that the washing water and the stabilizing solution contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent 345,172A1 can be mentioned.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water is calculated, the amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and water is supplied to the bleaching tank in proportion to the amount of evaporation.
, No. 3-249644, No. 3-24 @ 645, and No. 3-249646, the evaporation correction method using a liquid level sensor or an overflow sensor is preferable.
Tap water may be used as water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

The various processing solutions in the present invention are used at 10 ° C. to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. 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 processing the color negative film and the color paper using the same processing liquid, the cost of the processing machine can be reduced and the processing can be simplified.

Next, the silver halide grains used in the present invention will be described. Preferred silver halide grains in the present invention are silver chloride and silver chlorobromide, silver chloroiodide and silver chloroiodobromide having a silver chloride content of 60 mol% or more, and more preferably 70 mol% of silver chloride. % To 99 mol%, particularly preferably silver halide grains having a silver chloride content of 90 mol% to 99 mol%. Silver halide grains that can be used in combination in the present invention are silver chlorobromide, silver chloroiodide, silver chloroiodobromide having a silver chloride content of less than 60 mol%, or silver bromide, silver iodide, and silver iodobromide. is there. Other silver salts, such as silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver, may be contained as separate grains or as part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a silver chloride content of at least 30 mol%, preferably at least 60 mol% are desirable. When the development is moderately suppressed, it is preferable to contain 0.1 to about 40 mol% of silver iodide. The preferred silver iodide content varies depending on the intended light-sensitive material, but is generally in the range of 1 to 15 mol%. Further, in the present invention, European Patent No. 0,534,395A1,
No. 0,584,817 A1, U.S. Pat.
No. 3,951, No. 4,386,156, No. 5,2
It is also preferable to use high silver chloride tabular silver halide grains described in JP-A-64,337 and the like.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in a layered or non-layered form inside and / or on the surface of silver halide grains. The halogen composition of the localized phase is preferably at least 10 mol% to 90 mol%, more preferably at least 20 mol% to 90 mol%, in terms of silver bromide content. The silver bromide content of the localized layer of silver bromide is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis”, Maruzen) or the like. can do. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase epitaxially grown at the corners of the grains.

The silver halide emulsion used in the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. The typical one is Tokuboku Sho 43
-13162, JP-A-61-215540, JP-A-60-222845, JP-A-60-143331,
JP-A-61-75337, JP-A-60-222844
Issue. In order to give a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. These examples are disclosed in JP-A-59-133540 and JP-A-58-108526.
No. 199,290A2, Japanese Patent Publication No. 58-2
No. 4772, and JP-A-59-16254. In the case of a bonding structure, it is naturally possible to combine silver halides, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a bonding structure.

In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment. In the case of silver halide grains in which two or more silver halides exist as mixed crystals or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032.
Particularly, an emulsion having a high uniformity with a variation coefficient of the halogen composition distribution of 20% or less is preferable. It is important to control the halogen composition near the surface of the grains. Increasing the silver iodide content near the surface or increasing the silver chloride content can be selected depending on the purpose because the dye adsorption property and the developing speed are changed.

The silver halide grains used in the present invention may be normal crystals which do not contain twin planes, but can be edited by the Photographic Society of Japan, "Basics of photographic engineering, silver salt photography" (Corona), p. 163 (Showa 54). Example, two parallel twin planes
It can be selected and used according to the purpose from parallel multiple twins containing two or more, non-parallel multiple twins containing two or more non-parallel twin planes, or the like. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, Japanese Patent Publication No. 55-42737,
Dodecahedral particles having a (110) plane disclosed in Japanese Patent Application No. 0-222842 can be used. In addition, Jour
nal of Imaging Science, Vol. 30, p. 247 (1986
) Can be selected and used according to the purpose. (100)
Such as a tetrahedral particle in which the plane and the (111) plane coexist in one particle, a particle in which the (100) plane and the (110) plane coexist, or a particle in which the (111) plane and the (110) plane coexist.
Particles in which one surface or many surfaces coexist can be selected and used depending on the purpose.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio greater than 1 can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Practice.
(1930)), p. 131; Photographic Science and Engineering (Gutoff Photogr)
aphic Science and Engineering), Vol. 14, 248-
257 (1970); U.S. Pat. No. 4,434,226
No. 4,414,310, No. 4,433,04
8, No. 4,439,520 and British Patent No. 2,439.
It can be prepared by the method described in JP-A-112,157 or the like. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, which is described in detail in U.S. Pat. No. 4,434,226 cited above. . 80% of the sum of all projected areas of grains
The average aspect ratio of the particles occupying the above is 1 or more and 1
Less than 00 is desirable. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. The shape of the main plane of the tabular grains can be selected from triangles, hexagons, circles and the like. A regular hexagon in which the lengths of the six sides of the main plane are substantially equal as described in U.S. Pat. No. 4,797,354 is a preferred form.

Although the equivalent circle diameter of the projected area is often used as the grain size of the tabular grains, US Pat.
Particles having an average diameter of 0.6 microns or less as described in JP-A No. 8,106 are preferable for high image quality. Also,
Emulsions having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617 are also preferred. It is preferable that the thickness of the tabular grains be 0.5 μm or less and 0.01 μm or more, more preferably 0.3 μm or less and 0.01 μm or more, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable. Particles containing no dislocation lines at all,
It is preferable to select a particle containing several dislocations or a particle containing many dislocations according to the purpose. It is also possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them all over the grains, or to introduce them only into specific portions of the grains,
For example, dislocations can be introduced only in the fringe portion of the particle, and the like can be selected. The introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of normal crystal grains or irregular grains typified by potato-like grains. The silver halide emulsion used in the present invention is disclosed in European Patent No. 96,727B1.
No. 64,412B1 and the like, or a process for rounding particles, or a method disclosed in West German Patent No. 2,30.
The surface may be modified as disclosed in JP-A-6-447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532, JP-A-60-22132
0 or U.S. Pat. No. 4,643,966. The grain size of the emulsion used in the present invention can be evaluated by the equivalent circle diameter of the projected area using an electron microscope, the equivalent sphere diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent sphere diameter of the volume by the Coulter counter method. It can be used by selecting from a wide range from ultrafine particles having a sphere equivalent diameter of 0.01 μm or less to coarse particles exceeding 10 μm. Preferably, grains having a size of 0.1 to 3 microns are used as photosensitive silver halide grains. The emulsion used in the present invention may be a polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution, depending on the purpose. In some cases, a variation coefficient of a diameter equivalent to a projected area circle of a particle or a sphere equivalent diameter of a volume is used as a scale representing a size distribution. When a monodisperse emulsion is used, the coefficient of variation is 2
It is preferable to use an emulsion having a size distribution of 5% or less, more preferably 20% or less, and still more preferably 15% or less. In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Ballmontell (P.G.
lafkides, Chimie et Physique Photographique Paul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion Ch.
emistry (Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikuman et al., Focal Press (VL Ze)
likman et al, Makingand Coating Photographic Emuls
ion, Focal Press, 1964) and the like. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. US Pat. No. 4,334,012, a method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion.
No. 4,301,241 and 4,150,99
No. 4 is optionally preferred. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. It is also effective in some cases to add fine particles having various halogen compositions to modify the surface.

A method for converting most or a very small portion of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,771.
Nos. 142,900, European Patent Nos. 273,429 and 273,430, and West German Patent 3,819,241.
And the like. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, UK Patent No. 1,469,480 and US Patent No. 3,650,7
No. 57, No. 4,242,445, the particle forming method in which the concentration is changed or the flow rate is changed is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a complicated function of the addition time. A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in U.S. Pat.
Nos. 996,287, 3,342,605, 3,415,650, 3,785,777, West German Patent 2,556,885, and 2,555.
364 can be used. Silver halide solvents are useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening can be carried out by adding the whole amount to the dispersion medium in the reactor before adding the silver salt and the halide salt, or adding the halide salt, the silver salt or the deflocculant and adding the silver salt and the deflocculant in the reactor. Can also be introduced.

Examples of these include ammonia, thiocyanate (rodancali, rhodamonium ammonium, etc.), and organic thioether compounds (for example, US Pat. No. 3,574,574).
No. 628, No. 3,021, 215, No. 3,05
No. 7,724, No. 3,038,805, No. 4,2
No. 76,374, No. 4,297,439, No. 3,
Compounds described in 704,130, 4,782,013 and JP-A-57-104926. ) And thione compounds (for example, JP-A-53-82408 and JP-A-55-77).
No. 737, U.S. Pat. No. 4,221,863, etc .;
No. 9) and JP-A-57-202.
Mercapto compounds and amine compounds (for example, JP-A-54-100717) capable of promoting the growth of silver halide grains described in JP-A-531. Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion used in the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol ,
Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. it can.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin Bull. Soc. Sci. Photo. Japan. N
o. 16. Enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used. JP-A-1-158426
The use of the low-molecular-weight gelatin described in (1) is preferable for preparing tabular grains. The silver halide emulsion is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of the washing can be carried according to the purpose, but 5-50
It is preferable to carry in the range of ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. Although the pAg at the time of washing can be selected according to the purpose, it is preferable to carry the pAg between 5 and 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing a silver halide emulsion, for example,
Time, desalination process, chemical sensitization, salt of metal ion before coating
It is preferable depending on the purpose. Dope particles
In the case of particle formation, modification of the particle surface or chemical
When used as a sensitizer, after grain formation and before completion of chemical sensitization
It is preferred to add. When doping the whole grain
Only the core of the particles, or only the shell, or
Doping only on the epitaxial part or only on the base particles
You can also choose the way to take Mg, Ca, Sr, Ba, A
1, Sc, Y, La, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b, Bi, etc. can be used. These metals are
Monium salt, acetate, nitrate, sulfate, phosphate, hydroxide
Alternatively, it may be dissolved when forming particles such as a six-coordinate complex salt and a four-coordinate complex salt.
Any form of salt that can be added can be added. For example, C
dBr _2,CdCl_Two, Cd (NO_Three)_Two, Pb (N
O_Three)_Two, Pb (CH_ThreeCOO)_Two, K_Three｛Fe (C
N)₆｝, (NH_Four)_Four｛Fe (CN)₆｝, K_ThreeIrC
l₆, (NH_Four)_ThreeRhCl₆, K_FourRu (CN)₆Etc.
I can do it. Halo is preferably used as the ligand of the coordination compound.
Gen, H_TwoO, cyano, cyanate, thiocyanate,
Nitrosyl, thionitrosyl, oxo, carbonyl
You can choose from. These are one kind of metal compounds
May be used alone or in combination of two or more
May be used.

In some cases, a method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present. The silver halide grains used in the present invention have at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization. It can be applied in any step of the production process of the silver emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. A type in which a chemical sensitizing nucleus is embedded inside the grain,
There is a type that fills a shallow position from the particle surface, or a type that forms a chemical sensitizing nucleus on the surface. In the emulsion used in the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose.

Chemical sensitization which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, Fourth Edition, Macmillan Company. Published, 197
7 years, (TH James, TheTheory of the Photographi
c Process, 4th ed, Macmillan, 1977), using active gelatin as described in pages 67-76, and also by Research Disclosure Item 1200.
8 (April 1974); Item 13452 (1975)
June); Item 307105 (November 1989); U.S. Pat. Nos. 2,642,361 and 3,297,446.
No. 3,772,031 and No. 3,857,71
No. 1, No. 3,901,714, No. 4,266,0
18 and 3,904,415, and British Patent 1,315,755 as described in pAg.
The reaction can be performed with sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers at 5 to 10, pH 5 to 8 and a temperature of 30 to 80 ° C.

In the sulfur sensitization, an unstable sulfur compound is used, and specifically, thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines, mercaptos, thioamides, thiohydantoins, 4-oxooxazolidine-2-thiones, di- or polysulfides, polythioic acid Salts and elemental sulfur, and U.S. Patent Nos. 3,857,711 and 4,26
Known sulfur-containing compounds described in 6,018 and 4,054,457 can be used.
Sulfur sensitization is often used in combination with noble metal sensitization. The preferred amount of the sulfur sensitizer used for the silver halide grains is 1 × 10 ⁻⁷ to 1 × 10 per mol of silver halide.
^-3 mol, more preferably 5 × 10 ⁻⁷ to 1 × 1.
^0-4 moles.

In the selenium sensitization, a known unstable selenium compound is used. For example, US Pat. No. 3,297,44
No. 6,297,447 and the like, and specific examples thereof include colloidal metal selenium and selenoureas (for example, N, N-dimethylselenourea, tetramethylselenourea). Urea, etc.), selenoketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide) And selenium compounds such as selenophosphates (for example, tri-p-tolyl selenophosphate). It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization. The amount of the selenium sensitizer used depends on the type of selenium compound and silver halide grains used, the conditions of chemical ripening, and the like.
^-8 to 10 ^-4 mol, preferably about 10 ^-7 to 10 ^-5 mol is used.

The tellurium sensitizers used in the present invention include Canadian Patent No. 800,958 and British Patent Nos. 1,2.
No. 95,462, No. 1,396,696, Japanese Patent Application No. 2
Compounds described in JP-A-333819 and JP-A-3-131598 can be used. In precious metal sensitization,
Noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdCX ₆ or R ₂ PdX ₄ .
Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom. Specifically, K ₂ PdCl ₄ ,
(NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂
PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

The emulsion used in the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol per mol of silver halide;
More preferably, it is 5 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol. The preferred range of the palladium compound is 5 × 10 ^-7 to 1
× 10 ^-3 mol. A preferable range of the thiocyan compound or the selenocyan compound is 1 × 10 ^{−6 to} 5 × 10 ^−2.
Is a mole. It is preferred that the silver halide emulsion is subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization is referred to as a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a pAg 1 to 7 low pAg atmosphere called silver ripening, or a high pH ripening.
Either a method of growing in a high pH atmosphere of pH 8 to 11 or a method of ripening can be selected. Also, two or more methods can be used in combination. As the reduction sensitizer, a known reduction sensitizer such as stannous salt, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidine sulfinic acid, silane compounds, and borane compounds is used. And 2
Stannous chloride, aminoiminomethanesulfinic acid (common name: thiourea dioxide), dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers which can be used in combination of two or more compounds.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitizers are described in U.S. Pat. Nos. 2,131,038 and 3,41.
Nos. 1,914 and 3,554,757,
No.-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. It is preferable to use an oxidizing agent for silver during the emulsion manufacturing process. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide, and adducts thereof (eg, Na ₂ BO ₂ .H ₂ O).
_{2 · 3H 2 O, 2Na 2} CO 3 · 3H 2 O 2, Na 4 P
_{2 O 7 · 2H 2 O 2} , 2Na 2 SO 4 · H 2 O 2 · 2H
₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C)
₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ {Ti (O ₂ ) C ₂ O ₄ } .3H ₂ O, 4K ₂ S
O ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃ ｛V
O (O ₂ ) (C ₂ H ₄ ) ₂ .6H ₂ O｝, permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr)
Oxyacid salts such as ₂ O ₇ ), halogen elements such as iodine and bromine,
Perhalates (eg, potassium periodate), salts of high valent metals (eg, potassium hexacyanoferrate)
And thiosulfinic acid salts. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) Is given as an example. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (1-phenyl-5-mercaptotetrazole, 1-
(5-methylureidophenyl) -5-mercaptotetrazole and the like); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes and tetraazaindenes (particularly, 4-hydroxy-6
-Methyl (1,3,3a, 7) tetraazaindene),
Many compounds known as antifoggants or stabilizers, such as pentaazaindenes, can be added. For example, U.S. Pat.
No. 982,947 and JP-B-52-28660 can be used. One of the preferred compounds is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before, during and after grain formation, during the washing step, during dispersion after washing, during chemical sensitizers, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like. The dyes used include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole A nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be used.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No. 3,666,480, No. 3,672,898, No. 3,679,428, No. 3,703,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-4936, 53-12
No. 375, JP-A-52-110618, JP-A-52-10
No. 9925. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, this is done after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A Nos. 969 and 113/92, spectral sensitization can be carried out simultaneously with chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A-58-113,92.
It can be carried out prior to chemical sensitization as described in No. 8, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, these compounds can be added separately, i.e., some of these compounds can be added prior to chemical sensitization and the remainder can be chemically modified. It is also possible to add after sensitization, see U.S. Pat.
At any time during the formation of silver halide grains, including the method disclosed in JP-A-183,756. The addition amount is from 4 × 10 ^-6 to 8 × 10 per mol of silver halide.
^-3 mol can be used, but when the silver halide grain size is more preferably 0.2 to 1.2 .mu.m, about 5.times.10.sup.- ⁵ to
2 × 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material used in the present invention, but other various additives can be used according to the purpose. These additives are described in more detail in Research Disclosure Item 1
7643 (December 1978), Item 18716
(November 1979) and Item 307105 (1
(November, 989), and the relevant locations are summarized in the table below. In the present invention, the silver halide emulsion comprising the silver halide grains described above is preferably used as a silver halide emulsion having a silver chloride content of 6 as described above.
High silver chloride grains of 0 mol% or more. Even in the high silver chloride grains, a composition having an aspect ratio (a value obtained by dividing a circle equivalent diameter of the projected area by a grain thickness) of at least 50% of the total projected area of the silver halide grains is 2 to 25, Silver chlorobromide,
Tabular silver halide grains composed of silver chloroiodide or silver chloroiodobromide. Hereinafter, the silver halide emulsion comprising the high silver chloride tabular grains will be described in detail. The main plane is (1
The high silver chloride tabular silver halide emulsion of the (00) plane is disclosed in U.S. Pat. Nos. 4,063,951 and 4,386,156.
No. 5,264,337, JP-A-7-14652
It can be prepared by the method disclosed in No. 2. It can also be prepared by the method described below,
In the present invention, this method is the most preferred method for preparing a high silver chloride tabular silver halide emulsion. The tabular grain emulsion containing high silver chloride of the present invention can be produced as follows.

1) Nucleation process The tabular nuclei serving as nuclei of the tabular grains have a high generation ratio under conditions where lattice defects are likely to be introduced. As a method for obtaining plate nuclei with high reproducibility and a high generation ratio, a method utilizing halogen conversion of the generated nuclei is effective. In this method, silver halide nucleation is first performed, and subsequently, halogen conversion for forming a hardly soluble silver halide is performed to perform halogen conversion. More specifically, the nucleus formed at the time of nucleation has a halogen composition structure of, for example, (AgX ₁ | AgX ₂ ) or (A
gX ₁ | AgX ₄ | AgX ₃ )
For example, an aqueous solution of a silver salt (hereinafter referred to as “Ag ⁺ solution”) and an aqueous solution of a halide salt (hereinafter referred to as “X ^- solution”) are simultaneously mixed and added, and the halogen composition of the X ^- solution is determined at the gap surface. It can be formed by changing discontinuously.
Alternatively, add the X ⁻ solution to the dispersion medium solution, then add the Ag ⁺ solution to form AgX ₁ , then add another X ⁻ solution, then add the Ag ⁺ solution, and add (AgX ₁ | AgX ₂ ) structure or a combination thereof. AgX ₁ and AgX ₂ and AgX ₁ and Ag
X ₄ , AgX ₄ and AgX ₃ have a Cl ⁻ content or Br ⁻
The contents differ by 25-100 mol%, preferably by 50-100 mol%, more preferably by 75-100 mol%.
Further / or the I ^- content differs by 5-100 mol%, preferably 10-100 mol%, more preferably 30-100 mol%. In addition, there can be mentioned an embodiment in which the Cl ^- content difference or the Br ^- content difference is in accordance with the above-mentioned rules, and the I ^- content difference is 0 to 5 mol%. Nucleus size 0.15μm
The following is preferable, and 0.01 to 0.1 μm is more preferable.
The molar ratio of AgX ₁ : AgX _{2 in} the case of (AgX ₁ | AgX ₂ ) and the A of (AgX ₁ | AgX ₄ | AgX ₃ )
The molar ratio of gX ₁ : AgX ₄ : AgX ₃ was changed variously,
The molar ratio that gives the most preferred embodiment of the present invention can be selected and used. In order to perform the above-mentioned halogen conversion more uniformly, various methods other than the simultaneous addition of the aqueous silver salt solution and the aqueous halogen salt solution to the reaction vessel can be considered.

As a first method, a mixer is provided outside a reaction vessel having an aqueous protective colloid solution for causing crystal growth of silver halide grains, and an aqueous solution of a water-soluble silver salt and a water-soluble halogen are provided in the mixer. An aqueous solution of a salt and an aqueous solution of a protective colloid are supplied and mixed, and immediately supplied to a reaction vessel, whereby crystal growth of silver halide grains can be performed in the reaction vessel. At this time, it is important that no silver salt aqueous solution and halogen salt aqueous solution are added to the reaction vessel at all, and that the protective colloid aqueous solution (including silver halide particles) in the reaction vessel is also circulated to the mixer at all. That is not. The fine particles formed by this method preferably have an average equivalent sphere diameter of 0.05 μm or less, and more preferably have an average sphere equivalent diameter of 0.05 μm or less.
It is 2 μm or less, most preferably 0.01 μm or less. Details of such a method are disclosed in
Issue can be referred to. In the second method, at least one halide ion releasing agent represented by the following formula (Z) can be used. Formula (Z) Y—C (R ₁ ) (R ₂ ) -X In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom;
Represents an organic group having a Hammett σp value larger than 0, and R ₁
And R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, aryl group or a group represented by Y. However, Y and R ₁ may be closed to form a heterocyclic ring. For details, see, for example,
285,942, JP-A-2-68538, JP-A-6-686
Reference can be made to each specification of No. 11781. In order to make the above-mentioned halogen conversion uniform, it is preferable to stir the stirrer in the reaction vessel as fast as possible. However, high-speed stirring always involves the problem of foaming. As a method for solving the above problem, there is a defoaming technique, and there are two methods, physical mechanical defoaming and chemical defoaming (antifoaming agent), in terms of specific enforcement.

The physical mechanical defoaming technology is disclosed in Japanese Patent Application Laid-Open No. 7-2190.
As described in specification No. 92, a reaction vessel having a dimple structure or a protrusion structure in which a large number of dimples or protrusions are arranged in at least a part of the inner wall of the reaction vessel or at least a part of the internal space of the reaction vessel is used. be able to. In addition, as the chemical defoaming agent, an organopolysiloxane containing a polyalkylene oxide group can be used. For details, reference can be made to JP-A-8-043976. Further, JP-A-7-028
No. 183, No. 7-098482, a copolymer of PPO and acrylamide having a PPO content of 70% or more, a mixture of a PPO-only side-chain polymer and a PEO-only side-chain polymer. PPO content is 7.0
% Or more can be used as an antifoaming agent. The atmosphere of the dispersion medium solution at the time of nucleation must be a {100} plane forming atmosphere. Cl ^- in the case of the formation performed in excess concentration under most normal conditions (pC10.8~3.0, pH2
9) are {100} plane forming atmospheres. In the range of pH 1 to 7, the higher the pH, the higher the pCl
The higher the value, the higher the defect formation frequency. Where p
A ^- [mol / l Cl] Cl = -log.

The dispersion medium concentration of the dispersion medium solution at the time of nucleation is 0.1.
It is preferably from 10 to 10% by weight, more preferably from 0.3 to 5% by weight. The pH is preferably 1 to 10, and more preferably 2 to 8.
The temperature is preferably from 10 to 80C, more preferably from 30 to 60C. The excess Br ⁻ concentration is preferably 10 ⁻² mol / l or less, more preferably 5 × 10 ⁻³ mol / l or less. The excess Cl ^- concentration is preferably pCl = 0.8 to 3.0,
1.2 to 2.8 are more preferred. During nucleation, a silver salt solution added to enable uniform nucleation and / or X
^- it can be included dispersion medium salt solution. The concentration of the dispersion medium is preferably 0.1% by weight or more, more preferably 0.1 to 2% by weight, even more preferably 0.2 to 1% by weight. Molecular weight 300
More preferred is a low molecular weight gelatin of from 0,000 to 60,000, preferably 8,000 to 40,000. More preferably, the Ag ⁺ solution and the X ^- solution are added directly to the solution through a porous material addition system having 3 to 10 ¹⁵ , preferably 30 to 10 ¹⁵ , pores. Details are described in JP-A-3-21339 and 4-193.
336 and JP-A-6-086923 can be referred to. As for gelatin, the frequency of formation of the defect is higher in gelatin having a lower methionine content. From the gelatin having a methionine content of 1 to 60 μmol / g, the most preferable gelatin can be selected and used depending on the case.

Excess X ^- salt concentration during nucleation, or excess A
By lowering the g ⁺ salt concentration, the mixing ratio of twin particles can be reduced. An aqueous solution of a silver salt and a solution of a halide salt (hereinafter, referred to as an X ^- salt) are added to a dispersion medium solution containing at least a dispersion medium and water while stirring to form nuclei. The Cl ^- concentration in the dispersion medium solution at the time of nucleation is 4
X 10 ^-2 mol / l or less is preferable, and the Ag ⁺ concentration is preferably 10 ^-2 mol / l or less. The pH is preferably 2 or more, more preferably 5 to 10. Gelatin concentration is 0.1
To 3% by weight, more preferably 0.2 to 2% by weight. Although the temperature at the time of nucleation is not limited, usually 10 ° C. or higher is preferable, and 20 to 70 ° C. is preferable. After nucleation, physical ripening is performed to eliminate non-tabular grains and grow the tabular grains. The addition rate of the aqueous silver salt solution is preferably 0.5 to 20 g / min, more preferably 1 to 15 g / min, per liter of the container solution. There is no particular limitation on the pH of the container solution, but usually pH 1 to 11, preferably pH 3 to 10 is used.
Most preferred depending on the combination of excess silver salt concentration, temperature, etc.
A pH value can be selected and used.

2) Ripening process It is not possible to produce only tabular grain nuclei during nucleation. Therefore, tabular grains are grown by Ostwald ripening in the next ripening step, and other grains are extinguished. The aging temperature is 40 ° C or higher, preferably 45 to 90 ° C, more preferably 50 to 80 ° C. It is preferable to ripen in a (100) plane forming atmosphere. The aging conditions are preferably selected from the nucleation condition range. The ripening rate usually increases with increasing pH in the pH range of 1 to 6,
In the region of Cl1 to Cl3, it becomes faster as the Cl ^- concentration increases. In the present invention, a silver halide solvent can be used at the time of ripening, but more preferably, substantially no coexistence. Here, substantially means the silver halide solvent concentration d _0.
It is preferably d ₀ ≦ 0.5 mol / liter, more preferably d ₀ <0.1 mol / liter, more preferably d ₀ <0.
Refers to 02 mol / l. Examples of the silver halide solvent include NH ₃ , thioethers, thioureas, thiocyanic acids, organic amine compounds, and tetrazaindenes. Preferred are thioethers, thioureas and thiocyanic acids.

The pH during ripening is 1 to 12, preferably 2 to
8, more preferably 2 to 6. As the dispersing medium for nucleation, ripening and growth, conventionally known dispersing media for silver halide emulsions can be used. In particular, the methionine content is preferably 0 to 50 μmol / g, and more preferably 0 to 50 μmol / g.
Gelatin of ３０30 μmol / g can be preferably used. When the gelatin is ripened and used during growth, thinner tabular grains having a uniform diameter size distribution are formed,
preferable. Also, Japanese Patent Publication No. 52-16365, Journal of the Photographic Society of Japan, Vol. 29 (1), 17, 22 (1966), Vol. 30 (1), 10, 19 (1967), Vol. 30 (2), 17 (1967), 33 (3), 24
(1967) can be preferably used as a dispersion medium. Also, European Patent 0534395
The crystal habit controlling agent described in A1 can be used in combination. The concentration of the dispersion medium is preferably 0.1 to 10% by weight, and the control agent can be used preferably at 10 ^-1 to 10 ^-6 mol / l, more preferably at 10 ^-2 to 10 ^-3 mol / l. . These can be added at any time from before nucleation to the end of growth. It can be added to the existing dispersion medium in the form of additional addition, or can be added after the existing dispersion medium is removed by centrifugation or the like.

3) Growth process After the ratio of tabular grains is increased by ripening, a solute is then added to further grow the tabular grains. As the method of adding the solute, 1) a solution addition method (a method of adding an aqueous solution of a silver salt and an aqueous solution of a halide salt), 2) a method of forming silver halide fine particles in advance and adding the fine particles, and 3) a combination of both methods Method. In order to grow the tabular grains preferentially in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range that does not undergo Ostwald ripening. That is, it is necessary to control the concentration at a low supersaturated concentration with high accuracy. The method 2) is more preferable to make this possible. 0 for fine grain emulsion addition method.
A silver halide fine grain emulsion having a diameter of 15 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously,
It can also be added intermittently. The fine particle emulsion can be continuously prepared by supplying an aqueous solution of a silver salt and an aqueous solution of a halide salt in a mixer provided in the vicinity of the reaction vessel, and can be immediately and continuously added to the reaction vessel. And then added continuously or intermittently. The fine particles preferably do not substantially contain twin particles. "Substantially not contained" means that the twin particle number ratio is 5% or less, preferably 1% or less, and more preferably 0.1% or less.
% Or less.

The halogen composition of the fine particles can be silver chloride, silver bromide, silver iodide, or a liquid crystal of two or more of them. The solution conditions during the grain growth are the same as the conditions during the ripening. Both are processes for growing tabular grains by Ostwald ripening and eliminating other fine particles, and are mechanically the same. For details of the method of adding the fine grain emulsion, reference can be made to JP-A-4-03544, JP-A-5-281640 and JP-A-1-183417. In order to form fine particles substantially free of twin planes, an aqueous silver salt solution and an aqueous halide salt solution are added simultaneously with an excess halide ion concentration or excess silver ion concentration of preferably 10 ⁻² mol / l or less. What is necessary is just to add and form by a method. The fine particle formation temperature is preferably 50 ° C or lower, more preferably 5 to 40 ° C,
0-30 degreeC is more preferable. The dispersion medium preferably has a molecular weight of 2,000 to 6 × 10 ⁴ , more preferably 5,000 to 6,000.
4 × 10 ⁴ low molecular weight gelatin preferably 30% by weight
Gelatin occupying 60% by weight or more, more preferably 80% by weight or more is preferred. The concentration of the dispersion medium is preferably 0.2% by weight or more, more preferably 0.5 to 5% by weight.

During the nucleation and growth processes, a silver halide solvent is used.
Can be used together, but practically NH _ThreeDo not coexist
Is preferred. Also, when growing, NH_ThreeDo not coexist
Is preferred. Here, “substantially” means NH_ThreeDensity Z₁But
Z₁≤0.5 mol / liter, more preferably Z₁<0.1
Mol / liter, more preferably Z₁<0.02 mol / l
Means a title. For nucleation and growth processes
NH_ThreeAgX solvents other than
preferable. Here, “substantially” refers to the Z₁Same as concentration regulation
It is. NH_ThreeAgX solvents other than thioate
Thioureas, thiocyanates, organic amine compounds
Substances, antifoggants such as tetrazaindene compounds
Thioethers and thioureas
And thiocyanates. The halogen composition during growth is
Liquid crystal of silver chlorobromide, silver chloroiodide, and silver chlorobromoiodide
Can be. In the case of silver chlorobromide, the compound ions are preferably
Is from 1 mol% to 20 mol%, more preferably 1 mol%.
% To 10 mol%, most preferably 2.0 mol%
To 10 mol%. In the case of silver chloroiodide, iodide
The amount of the ions is preferably 0.001 mol% to 1 mol%.

During the grain formation, dislocation lines can be introduced into the grains by a halogen composition gap method, a halogen conversion method, an epitaxial growth method or a combination thereof. Pressure fogging characteristics, reciprocity characteristics, and color sensitization characteristics are further improved and are preferable. Regarding this, JP-A-63-2
20238, 64-26839, JP-A-2-1276
35, 3-189644, 3-175440, 2
-123346, European Patent 0460656A1 Journa
l of Imaging Science, 32, 160-177 (19
88) can be referred to. The obtained particles may be used as host particles to form epitaxial particles. Further, particles having dislocation lines therein may be formed using the particles as a core. In addition, the grains may be used as a satuplate, and silver halide layers having a different halogen composition from the substrate may be laminated to produce grains having various known grain structures. Regarding these, the description in the following literature can be referred to. Further, a shallow inner latent emulsion may be formed using the tabular grains as a core. Also, core / shell type particles can be formed. This is described in JP-A-59-133542, 6
No. 3-151618, U.S. Pat. No. 3,206,313
No. 3,317,322 and 3,761,276
Nos. 4,269,927 and 3,367,778 can be referred to.

As described above, the most important parameter for obtaining a silver halide grain having a high aspect ratio is pAg during ripening and growth, and the aspect ratio of the tabular grains in the present invention is 2 or more. 25 or less. The aspect ratio is preferably 3 or more and 25 or less, and more preferably 4 or more and 20 or less. The aspect ratio is preferably in the above range mainly due to the balance between sensitivity and pressure. The adjacent main surface edge length ratio is 10 or less, more preferably 5 or less, and still more preferably 2 or less. The projected area of the tabular grains accounts for 50% or more, more preferably 60%, and still more preferably 70% or more of the projected area of all grains. The thickness is 0.3 μm or less, preferably 0.3 μm.
2 μm or less.

As used herein, "aspect ratio" refers to the ratio of the thickness between major planes to the average edge length forming the major planes of the grains, and "major planes" substantially form cuboid emulsion grains. Of the crystal surface, the plane is defined as a set of parallel surfaces having the largest area, and the fact that the principal plane is a {100} plane can be determined by an electron diffraction method or an X-ray diffraction method. A substantially cuboid emulsion grain has a principal plane of $ 10.
Although it is formed from the {0} plane, it means that it may have 1 to 8 {111} crystal planes. That is, one to eight of the eight corners of the rectangular parallelepiped may have a rounded shape. "Average edge length" is defined as the length of one side of a square having an area equal to the projected area of each grain as viewed in a micrograph of the emulsion grain sample. $ 10
A method of adsorbing a sensitizing dye without inhomogeneity between grains by forming a salt which is less soluble than silver chloride on the surface of high silver chloride tabular grains having a main plane of 0 ° plane. Is the preferred method. Silver salts that are less soluble than silver chloride include silver bromide, silver iodide, silver iodobromide, silver thiocyanate, silver selenocyanate, or a mixed crystal thereof.
Silver bromide, silver iodide and silver iodobromide are preferred. The amount of the silver salt which is more insoluble than silver chloride is 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 3 mol% or less, based on the whole grains. 0.001 mol% or more.

As a method of making a silver salt less soluble than silver chloride exist on the surface of the tabular grains, a method of adding a water-soluble halide salt and a water-soluble silver salt having a corresponding composition by a double jet, a method of adding fine particles, And a method using a sustained release agent of bromide ion or iodide ion. In the method of adding a water-soluble halide salt and a water-soluble silver salt by double jet, even if an aqueous solution of a halide salt is diluted and added, halogen ions are added in a free state. There are limits to trying to reduce locality. On the other hand, a method of adding fine particles or a method using a sustained release agent is a preferable method for forming a salt which is less soluble than silver chloride on the surface of the particles without unevenness between the particles. When added as fine particles, the average equivalent sphere diameter of the fine particles is preferably 0.1 μm or less, and 0.06 μm or less.
m or less are more preferable. The fine particles are continuously prepared by supplying an aqueous solution of a silver salt and an aqueous solution of a salt capable of forming a silver salt having a lower solubility than silver chloride in a mixer provided in the vicinity of the reaction vessel, and immediately adding it to the reaction vessel. It can also be added after being prepared in a batch manner in another container in advance. A method using a sustained release agent is disclosed in
85942 and JP-A-6-011780.

There are no particular restrictions on the method for producing high silver chloride tabular grains having {111} plane surfaces effectively used in the present invention. As a specific example, it can be obtained by using adenine in combination during particle formation. The addition amount of adenine or a salt thereof can be used in the range of 10 ^-4 to 10 ^-2 mol per mol of silver halide, and is particularly preferably 5 × 10 ^{-4 to} 5 × 10 ^-3 mol. The timing of adding adenine or a salt thereof may be such that adenine or a salt thereof is present at any time during grain formation from the time of nucleation of silver halide grains to the end of physical ripening in the production process of a silver halide emulsion. Preferably, at least a portion is present from the beginning of formation. Once tabular high silver chloride grains are formed,
Adenine is no longer needed, but usually remains at least partially adsorbed on the particle surface. Compounds that exhibit a strong affinity for silver halide grain surfaces, such as spectral sensitizing dyes, can replace adenine, and thus adenine can be substantially washed and removed from the emulsion. Adenine is also well known as an excellent antifoggant, and it is beneficial that adenine remains in the emulsion.

Normal crystals (8) were prepared using adenine or a salt thereof.
In order to separately produce tabular grains and non-tabular grains and tabular grains, the initial stage of grain formation (at the time of so-called nucleation)
It is preferable to adjust the pH. The pH range at the time of nucleation at which tabular grains are obtained is from 4.5 to 8.5, preferably from 4.8 to 8.0, and more preferably from 5.0 to 7.0. At pH 8.5 or higher, normal crystals are formed, and at pH 4.5 or lower, non-tabular grains having non-parallel twin planes are formed. At the time of nucleation, the chloride concentration is preferably 0.05 to 0.12 molar.
Below 0.05 molar concentration, normal crystals are liable to be formed, and above 0.12 molar concentration, non-tabular grains increase. PH during particle growth
Is not particularly limited, but is preferably kept in the range of 4.5 to 8.5. The chloride concentration during grain growth is preferably 5 molar or less, particularly preferably 0.07 to 3 molar. The temperature at the time of particle formation in the present invention can be used in the range of 10 to 95 ° C, preferably 35 to 90 ° C. Derivatives other than adenine can also be effectively used for forming {111} tabular grains.

Examples of which are described in US Pat. No. 5,178,99.
No. 5,178, the compound described in claim 1 of claim 7;
No. 998, Nos. 5,185,239
And pyrimidines described in US Pat. No. 5,252,452 and 4-sphere ammonium compounds described in US Pat. No. 4,983,508. Preferred ranges of the aspect ratio, the main surface adjacent edge length ratio, the thickness, and the ratio of the projected area to the total projected area of the total grains of the {111} tabular grains are the same as those of the {100} tabular grains. In the present invention, tabular grains having a {100} plane as a main plane are more preferable than {111} tabular grains. In the present invention, the silver halide grains obtained through the final step of the production of the above-mentioned tabular silver halide grains have a silver chloride content of 60 mol% or more in the halogen composition. It is preferably at least 70 mol%, more preferably at least 80 mol%. The group VIII metal, In, Cd, Zn,
Metal ions such as Tl, Pb, Bi, Hg, Cu, Cr, Mo, and Re can be doped. Preferred as doped metal ions are Pb, Fe, Cr, Rh, I
r and Ru.

The silver halide emulsion used in the present invention is preferably subjected to chalcogenide sensitization and reduction sensitization represented by gold sensitization, sulfur and selenium sensitization.
As the selenium sensitizer used in the present invention, the selenium compounds exemplified above and disclosed in the conventionally known patents can be used. That is, the emulsion is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489,
It is preferable to use the compounds described in JP-A Nos. 4-025832 and 4-109240. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g., bis (3-chloro-
2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like.

The preferred types of unstable selenium compounds have been described above, but these are not limitative. Those skilled in the art will note that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to make them present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is effectively used. The non-labile selenium compound used in the present invention is disclosed in
No. 4553, Japanese Patent Publication No. 52-34492 and Japanese Patent Publication No. 5
The compound described in 2-34491 is used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof.

Regarding the selenium sensitization method, US Pat.
No. 574,944, No. 1,602,592, No. 1,623,499, No. 3,297,446,
No. 3,297,447, No. 3,320,069, No. 3,408,196, No. 3,408,197,
No. 3,442,653, No. 3,420,670
No. 3,591,385, French Patent No. 269
No. 3038, No. 2093209, Japanese Patent Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
No. 57-22090, JP-A-59-180536,
59-185330, 59-181337, 59-187338, 59-192241, 6
No. 0-150046, No. 60-151637, No. 61
-24638, JP-A-3-4221, JP-A-3-3
148648, 3-11838, 3-116
No. 132, No. 3-237450, No. 4-0166838
No. 4-025832, No. 4-032831, No. 4-109240, and further, British Patent No. 255846,
No. 861984 and HE Spencer et al., Journal
ofPhotographic Science, Vol. 31, 158-169
Page (1983). The silver halide photographic emulsion used in the present invention can achieve higher sensitivity and lower fog by using sulfur sensitization and / or gold sensitization in chemical sensitization. Particularly, in the silver halide emulsion of the present invention, it is the most preferable embodiment to carry out a combination of gold sensitization and sulfur sensitization together with selenium sensitization. Sulfur sensitization is usually performed by adding an ion sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain period of time. Further, gold sensitization is usually performed by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time.

For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-
Toluenethiosulfonate, rhodanine and the like can be mentioned. Other U.S. Pat. Nos. 1,574,944 and 2,
Nos. 410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955, German Patent 1,42.
No. 2,869, JP-B-56-24937, and JP-A-55-55.
Sulfur sensitizers described in -45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount is
It varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but is preferably from 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. . Chemical sensitization after the addition of the sensitizing dye is preferable in that the necessary amount of the sensitizer added becomes small. As a gold sensitizer for the above gold sensitization, even if the oxidation number of gold is +1,
It may be trivalent, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, the standard is preferably 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide.

In chemical ripening, there are no particular restrictions on the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. There is no need to provide
For example, the compound can be added at the same time as the initial stage (preferably) of chemical ripening or during the progress of chemical ripening, or at a different time. In addition, the compound may be added by dissolving the above compound in water or an organic solvent miscible with water, for example, a single solution or a mixed solution of methanol, ethanol, acetone or the like. It is preferred that the silver halide emulsion used in the present invention is reduction-sensitized during grain formation, after grain formation, and during chemical sensitizer or chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a pAg1 to 7 low pAg atmosphere called silver ripening or a method of ripening, a method of high pH ripening called pH 8 to 1.
Either the method of growing in a high pH atmosphere or the method of ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted. As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount.
The range of ^0-7 to ^10-3 mol is suitable. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion used in the present invention. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water, such as silver halide, silver sulfide, and silver selenide,
Further, a silver salt easily soluble in water such as silver nitrate may be formed. The oxidizing agent for silver may be inorganic or organic. These exemplified compounds are the same as described above. Preferred oxidants used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidants of thiosulfonates and organic oxidants of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.
The silver halide photosensitive material used in the present invention may have two or more kinds of photosensitive layers having different spectral sensitivities, and the spectral sensitivities are not limited to blue sensitivity, green sensitivity, and red sensitivity. As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are Research Disclosure Nos. 17643, 18716 and 30.
7105, and the relevant portions are summarized in the table below.

Types of Additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer 23 page 648 right column 866 page 2 Sensitivity enhancer 648 right column 3 Spectral sensitizer, page 23-24 page 648 right column-866-868 supersensitizer 649 page right column 4 Brightener 24 page 647 page right column 868 5 Antifoggant, page 24-25 page 649 Right column-page 868-870 Stabilizer 6 light absorber, page 25-26 page 649 right column-page 873 Filter dye, page 650 left column UV absorber 7 Stain inhibitor 25 page right column 650 page left column-right column Page 872 8 Dye image stabilizer Page 25 Page 650 Left column 872 9 Hardener 26 Page 651 Left column 874 to 875 10 Binder 26 Page 651 Left column 873 to 874 11 Plasticizer, lubricant 27 Page 651 right column page 876 12 coating aids, 26-27 page 650, right column 875-876 pp surfactant 13 Antistatic 27 page 650, left column 876-877 pages inhibitor 14 matting agent 878-879 pages present invention For other techniques and inorganic and organic materials can be used in the color photographic light-sensitive material used,
It is described in EP 436,938 A2 at the following places and in the patents cited below.

1. Layer structure: page 146, line 34 to 147
Page 25, line 2. Yellow coupler: page 137, line 35 to 146
Page 33, line 149, lines 21 to 23 3. Magenta coupler: page 149, lines 24 to 28; EP 421,453A1, page 3, lines 5 to
Page 25, line 55 4. Cyan coupler: page 149, lines 29 to 33; EP 432,804A2, page 3, line 28 to page 40, line 2. 5. Polymer coupler: 149 P. Lines 34-38; p. 113 of EP 435,334 A2, p.
Lines-page 123, line 37 6. Colored coupler: page 53, line 42-page 137, line 34, page 149, lines 39-45 7. Other functional couplers: page 7, line 1 Lines-page 53, line 41, page 149, line 46-page 150, line 3; EP 435,334A2, page 3, line 1-29
Page 50, line 8. Preservatives and fungicides: page 150, lines 25 to 28 9. Formalin scavenger: page 149, lines 15 to
Line 17 10. Other additives: page 153, lines 38 to 47; EP 421,453A1, page 75, line 21 to page 84, line 56, page 27, line 40 to Page 37 4
Line 0 11. Dispersion method: page 150, lines 4 to 24 12. Support: page 150, lines 32 to 34 13. Thickness and film properties: page 150, lines 35 to 49 Eye 14. Color development: page 150, line 50 to 151
Page 47, line 15. Desilvering step: page 151, line 48 to page 152, line 53 16. Automatic developing machine: page 152, line 54 to page 153, line 2 17. Rinse / stabilize step: page 153 3rd to 37th lines

The light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. The number of silver halide emulsion layers and non-light-sensitive layers is not particularly limited. A typical example is a silver halide photographic light-sensitive material having at least two color-sensitive layers comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Material, the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to either of red light and red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer and a green light-sensitive layer. A color layer and a blue-sensitive layer are provided in this order. The entire hydrophilic colloid layer including these color-sensitive emulsion layers is called a "photosensitive layer". Preferred maximum spectral sensitivity wavelengths of each layer are, for example, 420 to 480 nm for the blue-sensitive layer and 520 to 5 nm for the green-sensitive layer.
80 nm, and the red-sensitive layer is at 620 to 680 nm. A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) /, or BH / BL / GL / GH / RH / RL,
Alternatively, they can be installed in the order of BH / BL / GH / GL / RL / RH.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is further disposed, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.
Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat.
No. 3,271, No. 4,705,744, No. 4,7
07,436, JP-A-62-160448, JP-A-63-160448
It is preferable to dispose a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specification of JP-A-86850 adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

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EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention. (Example 1) 1) Preparation of emulsion 1-1) Preparation of emulsions A, B, C, D (silver iodobromide tabular emulsion) A tabular silver bromide having a thickness of 0.08 μm and a circle equivalent radius of 0.5 μm. The particles were prepared as seed crystals. 1.0 g of seed crystals containing 8 g of Ag
The solution was dissolved in 1 liter of distilled water, the pAg was adjusted to 8.2, the pH was adjusted to 5, the temperature was kept at 70 ° C, and the mixture was vigorously stirred. Subsequently, particles were formed in the following procedure. (I) AgNO ₃ (141 g) aqueous solution and KBr aqueous solution
Ag was added while keeping it at 8.4. (Ii) The temperature was lowered to 55 ° C., and a KI (4 g) aqueous solution was added at a constant flow rate. (Iii) AgNO ₃ (63 g) aqueous solution and KBr aqueous solution were pA
g was maintained at 8.9. The mixture was cooled to 35 ° C., washed with water by a conventional flocculation method, and adjusted to pH 6.0 and pAg 8.2 by adding 50 g of gelatin. The sum of the projected areas of tabular grains having an average equivalent sphere diameter of 0.7 μm and an aspect ratio of 3.0 or more occupied 70% of the total projected area.

This emulsion was subjected to gold-sulfur-selenium sensitization as follows. The temperature of the emulsion was raised to 64 ° C., and sensitizing dyes ExS-1, 2, and 3 described below were added in an amount and a ratio to obtain a desired spectral sensitivity, and then sodium thiosulfate 7.4 was added.
× 10 ^-6 mol / mol Ag, chloroauric acid 1.9 × 10 ^-6 mol / mol
Emulsion A was prepared by adding a mole Ag, potassium thiocyanate 1.9 × 10 ^-3 mole / mole Ag, and N, N-dimethylselenourea 1.5 × 10 ^-6 mole / mole Ag and performing optimal chemical sensitization.
I got Instead of sensitizing dyes ExS-1, 2, and 3, Ex
Emulsion B was used in the same manner as Emulsion A except that S-4, 5, 6, 7, 8 were used, Emulsion C was similarly used using ExS-4, 7, 8 and ExS-9 was used in the same manner. Emulsion D using
Was prepared.

1-2) Preparation of emulsions E, F, G, H (high silver chloride {100} tabular emulsion) In a reaction vessel, 1200 ml of an aqueous gelatin solution (deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) was added. Ag-1 solution (containing 14 g of AgNO ₃ , 0.8 g of the gelatin and 0.2 ml of a 1N HNO ₃ solution in 100 ml) and X-1 while maintaining the temperature at 40 ° C. Liquid (NaCl 6.9 g, gelatin 0.8 g, NaO
H1N solution (including 0.3 ml) was added simultaneously by 12 ml at 24 ml / min. After stirring for 2 minutes, the Ag-2 solution (100
2 g of AgNO ₃ , 0.8 g of the gelatin, 1N HNO ₃ solution in ml
0.2 ml) and X-2 solution (KBr 1.4 in 100 ml).
g, 0.8 g of the gelatin and 0.2 ml of 1N NaOH solution) were added simultaneously at a rate of 31 ml / min. After stirring for 1 minute, the Ag-1 solution and the X-1 solution were simultaneously mixed and added at 48 ml / min by 36 ml. NaCl aqueous solution (100 ml water with NaCl
(Including 10 g), the pH was adjusted to 4.5, and the temperature was raised to 75 ° C. After aging for 20 minutes, raise the temperature to 60
° C, and the pH was adjusted to 5.0.
-3 solution (containing AgNO ₃ 10 g in 100ml) and X-3 solution (containing NaCl 3.6 g in 100ml) C. D. J (co
ntrolled double jet). Flow at start of addition is 7
at a rate of 0.1 ml / min at a rate of 0.1 ml / min.
400 ml of solution g-3 was added.

Next, AgBr fine grains having an average equivalent sphere diameter of 0.03 μm were added in an amount of 0.2 mol% per mol of silver halide and ripened for about 5 minutes to complete halogen conversion. Next, a sedimentation agent was added, the temperature was lowered to 30 ° C., the precipitate was washed by settling, and an aqueous gelatin solution was added.
6.2, adjusted to pCl 3.0. The silver halide emulsion thus prepared had an average equivalent sphere diameter of 0.7 μm, an average silver chloride content of 95.6 mol%, an aspect ratio of 2.5 or more, and an adjacent side length ratio of 2.0 or less on the main plane. Of tabular grains of the total projected area of 7
The content was 5%. The average aspect ratio of the tabular grains was 6.5, and the average adjacent side length ratio on the main plane was 1.3.
This emulsion was subjected to gold-sulfur-selenium sensitization as follows. The emulsion was heated to 64 ° C., and the sensitizing dye ExS-
After adding 1, 2, and 3 in an amount and a ratio to obtain a desired spectral sensitivity, sodium thiosulfate (9.4 × 10 ⁻⁶ mol / mol Ag), chloroauric acid (3.3 × 10 ⁻⁶ mol) / Mol Ag, potassium thiocyanate 2.9 × 10 ^-3 mol / mol Ag, N,
2.7 × 10 ^-6 mol / mol Ag N-dimethylselenourea
Was added and the mixture was optimally subjected to chemical sensitization to obtain Emulsion E. Instead of sensitizing dyes ExS-1, 2, and 3, ExS-4, 5,
Emulsion F in the same manner as Emulsion E except that 6, 7, and 8 were used.
And Emulsion G using ExS-4, 7, and 8
Emulsion H was prepared in the same manner using ExS-9.

2) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
After drying 0 parts by weight and 2 parts by weight of Tinuvin P. 326 (manufactured by Ciba-Geigy) as an ultraviolet absorber,
After melting at 300 ℃, extrude from T-die, 140 ℃
, A 3.3-fold longitudinal stretching was performed, followed by a 3.3-fold transverse stretching at 130 ° C., and heat-setting at 250 ° C. for 6 seconds to obtain a 90 μm-thick PEN film. In addition, this PEN film has a blue dye, a magenta dye and a yellow dye (public technical report: I-1, described in Japanese Patent Publication No. 94-6023).
I-4, I-6, I-24, I-26, I-27, II
-5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support with which a winding habit was not easily formed.

3) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV irradiation treatment, and a glow discharge treatment on both surfaces, and then gelatin 0.1 g / m ² and sodium α- 0.01 g / m ^{2 of} sulfodi-2-ethylhexyl succinate, 0.04 of salicylic acid
g / m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ = CHSO
₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , an undercoat solution of polyamide-epichlorohydrin polycondensate 0.02 g / m ² (10 cc / m ² , using a bar coater), and an undercoat layer Was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

4) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer, and a slip layer were provided as a back layer on one surface of the support after the undercoating. 4-1) Coating of antistatic layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of a tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm (secondary aggregated particle diameter of about 0.08 μm) was prepared. 0.2 g / m ² , gelatin 0.05
g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² ,
Coated with poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005 g / m ² and resorcinol. 4-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g; Long axis 0.1
4 μm, uniaxial 0.03 μm, saturation magnetization 89 emu / g, Fe
^{+ 2} / Fe ⁺³ = 6/94, the surface of which has been treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide Was carried out with an open kneader and a sand mill), and C ₂ H ₅
C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied by a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent, and a magnetic recording layer having a thickness of 1.2 μm was applied. I got Silica particles (0.3 μm) and 3-
Abrasive aluminum oxide (0.15 μm) coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) was added at a concentration of 10 mg / m ² . Drying was carried out at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). X- light, the saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.3 × 10 ⁴
A / m and the squareness ratio were 65%.

4-3) Preparation of Sliding Layer Diacetylcellulose (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 ) mixture was applied. This mixture was melted at 105 ° C. in xylene / propylene glycol monomethyl ether (1/1), poured and dispersed in propylene glycol monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone. (Average particle size: 0.01 μm). Silica particles (0.3 μm) as a matting agent and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane as an abrasive (aluminum oxide (0.15%
μm) was added to give 15 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.
06 (5 mmφ stainless steel hard ball, load: 100 g, speed: 6 cm / min), static friction coefficient: 0.07 (clip method), and dynamic coefficient of friction between the emulsion surface and the sliding layer described later were 0.12, which were excellent characteristics.

5) Coating of photosensitive layer Next, on the side opposite to the back layer obtained above, layers having the following compositions were applied in a multi-layered manner to prepare a color negative film.
This is designated as Sample 101. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.08 Gelatin 0.70 Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.00 ExM-1 0.12 ExF-1 2.0 × ^10-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02 Third layer (intermediate layer) ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 0.70

Fourth layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.49 ExS-1 3.8 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.2 × 10 ^-4 ExC-1 0.17 ExC-2 0.02 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 1.10

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Emulsion A Silver 0.60 ExS-1 4.0 × 10 ^-4 ExS-2 2.1 × 10 ^-5 ExS-3 5.7 × 10 ^-4 ExC-1 0.14 ExC-2 0.02 ExC-3 0.03 ExC-4 0.090 ExC-5 0.02 ExC-6 0.008 Cpd-4 0.030 Cpd-2 0.05 HBS-1 0.10 Gelatin 0.75

Sixth layer (high-sensitivity red-sensitive emulsion layer) Emulsion A silver 1.30 ExS-1 2.5 × 10 ^-4 ExS-2 1.1 × 10 ^-5 ExS-3 3.6 × 10 ^-4 ExC-1 0.12 ExC-3 0.11 ExC-6 0.018 ExC-7 0.010 Cpd-2 0.050 Cpd-4 0.020 HBS-1 0.22 HBS-2 0.050 Gelatin 1.40 7th layer (middle layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.040 polyethyl Acrylate latex 0.15 Gelatin 1.10

Eighth layer (low-sensitivity green-sensitive emulsion layer) Emulsion B Silver 0.53 ExS-7 1.4 × 10 ^-4 ExS-8 6.2 × 10 ^-4 ExS-4 2.7 × 10 ^-5 ExS-5 7.0 × 10 ^-5 ExS-6 2.7 × 10 ^-4 ExM-3 0.410 ExM-4 0.086 ExY-1 0.068 ExY-5 0.006 HBS-1 0.30 HBS-3 0.015 Cpd-4 0.010 Gelatin 0.95

Ninth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion C Silver 0.94 ExS-4 4.8 × 10 ^-5 ExS-7 2.1 × 10 ^-4 ExS-8 9.3 × 10 ^-4 ExC-8 0.0020 ExM-3 0.115 ExM-4 0.035 ExY-1 0.008 ExY-4 0.010 ExY-5 0.0050 Cpd-4 0.011 HBS-1 0.13 HBS-3 4.4 × 10 ^-3 Gelatin 0.80

Tenth layer (high-sensitivity green-sensitive emulsion layer) Emulsion C Silver 1.30 ExS-4 4.5 × 10 ^-5 ExS-7 1.2 × 10 ^-4 ExS-8 5.3 × 10 ^-4 ExC-1 0.021 ExM-1 0.010 ExM-2 0.030 ExM-5 0.0070 ExM-6 0.0050 Cpd-3 0.017 Cpd-4 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

Eleventh layer (yellow filter layer) Yellow colloidal silver silver 0.010 Cpd-1 0.16 Solid disperse dye ExF-5 0.040 Solid disperse dye ExF-6 0.040 Oil-soluble dye ExF-7 0.008 HBS-1 0.60 Gelatin 0.60 12th layer (Low sensitivity blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-9 8.4 × 10 ^-4 ExC-1 0.03 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.75 ExY-3 0.40 ExY-4 0.040 Cpd- 2 0.10 Cpd-4 0.01 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 2.10

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion D silver 0.58 ExS-9 3.5 × 10 ^-4 ExY-2 0.070 ExY-3 0.070 ExY-4 0.0050 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 Cpd-4 0.02 HBS-1 0.075 Gelatin 0.55

14th layer (first protective layer) UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.001 ExF-9 0.002 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8 15th layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 0.04 B-2 (diameter 1.7 μm) 0.09 B-3 0.13 ES-1 0.20 gelatin 0.70 , Storage, processing, pressure resistance, fungicide
W-1 for improving antibacterial properties, antistatic properties and coatability
To W-3, B-4 to B-6, F-1 to F-
18, and iron salts, lead salts, gold salts, platinum salts, palladium salts,
Contains iridium and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.
700 ml of 7 ml and a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10)
In a milliliter pot mill, dye ExF-2 was added for 5.
0 g and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.
Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle size of the fine dye particles is
They were 0.24 μm, 0.45 μm and 0.52 μm. ExF
-5 is a microprecipitator described in Example 1 of EP-A-549,489A.
on) Dispersed by a dispersion method. The average particle size was 0.06 μm.

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6) Treatment After subjecting the sample 101 to wet exposure with white light, the following treatment A was carried out. (Processing A) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching and fixing 3 minutes 15 seconds 38 ° C Rinse (1) 40 seconds 35 ° C Rinse (2) 1 minute 00 seconds 35 ℃ Stability 40 seconds 38 ℃ Drying 1 minute 15 seconds 55 ℃

Next, the composition of the processing solution will be described. (Color developing solution) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 0.25 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium chloride 4.0 Disodium N, N-bis (sulfonateethyl) Hydroxylamine 8.6 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water and add 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05

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

(Bleach-fixing solution) (Unit g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Aqueous ammonium thiosulfate solution (700 g / liter) 240.0 ml ammonia water (27%) 6.0 Milliliter Add water 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.2 (Wash solution) Tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And OH type anion exchange resin (Amberlite IR-
400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2,4-triazole 1.3 1,4-Bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-Benzoisothiazolin-3-one 0.10 Add 1.0 liter of water, pH 8.5, and treat with yellow, magenta and cyan. The measurement was performed to determine the characteristic curve.

Next, Sample 102 was prepared in exactly the same manner as Sample 101 except that emulsions A, B, C and D were changed to emulsions E, F, G and H, respectively. Six samples obtained by cutting the sample 102 to a width of 35 mm were prepared and exposed to white light with a web. Only the processing time of the color development step of the development processing A is 45
Seconds, 55 seconds, 60 seconds, 65 seconds, 75 seconds, 90 seconds,
The development process was performed in exactly the same manner as in the composition of the processing solution and other steps, and a characteristic curve was obtained. As a result, it was found that the sample 101 subjected to the process A and the sample 102 subjected to the process with only the color development time of the process A changed to 65 seconds give almost the same maximum color density for yellow, magenta and cyan. Was. This processing is referred to as processing B-1.

The slope of the characteristic curve at an exposure amount that provides a color density of (maximum density−minimum density) / 2 for each of yellow, magenta, and cyan of the characteristic curve is θ, and an exposure that provides a color density of minimum density + 0.25 Let ε be the quantity
The log ε and tan θ are obtained and the sensitivity and the gradation are compared. The sensitivity and gradation for the yellow density of the sample 101 that has been subjected to the process A are represented by log ε _o (Y) and tan θ, respectively.
_{o As} (Y), let the sensitivity and gradation for the yellow density of another sample be log ε (Y) and tan θ (Y). The sensitivity difference ΔS (Y) and the gradation ratio r (Y) of the sample 101 that has been subjected to the process A with respect to the yellow density are defined as follows. Sensitivity difference: ΔS (Y) = log ε (Y) -log ε o (Y) gradation ratio: r (Y) = tan θ (Y) / tan θ o (Y) Similarly the magenta density [Delta] S (M) , R (M) and cyan density are defined as ΔS (C) and r (C). Since the characteristic curve obtained from the sample 101 on which the processing A was performed corresponds to the characteristic of a standard color negative film, it was used as a standard of sensitivity and gradation. It is preferable that ΔS is closer to 0 and r is closer to 1.

The sensitivity difference and gradation difference of the sample 102 on which the process B-1 was performed were as follows. ΔS (Y) = − 0.75, r (Y) = 1.56 ΔS (M) = − 0.70, r (M) = 1.48 ΔS (C) = − 0.69, r (C) = 1.40 This means that Sample 102 containing silver chloride emulsion has the same maximum color density at 1/3 color development time as Sample 101 containing silver iodobromide emulsion, but relatively low sensitivity. , The gamma is high and the dynamic range is narrow.

4-, which is the color developing agent of the pre-processing B-1
[N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate (referred to as PPD-1)
Is converted to N-ethyl-N- (β-sulfonamidoethyl)-
3-methyl-4-aminoaniline / 3/2 sulfate monohydrate (hereinafter referred to as PPD-2) and the compound D- of the present invention
3, D-12, D-14, D-40, D-79, D-9
3, Except that D-107 and D-118 were changed in the same number of moles, treatments B-2 to B-10 were performed in exactly the same manner.
From the obtained characteristic curves, the sensitivity difference ΔS and the gradation ratio r were determined for yellow, magenta, and cyan, respectively, as shown in Example 1. Table 1 shows the results.

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[Table 1] 試 料 Sample processing Color development Sensitivity difference Gradation ratio ΔS (Y) ΔS (M) ΔS (C) r (Y) r (M) r (C) ────────────────────────── ────────── 102 B-1 PPD-1 -0.69 -0.66 -0.64 1.50 1.48 1.39 Comparison 102 B-2 PPD-2 -0.78 -0.75 -0.71 1.60 1.61 1.51 Comparison 102 B-3 (3 ) -0.19 -0.25 -0.22 1.21 1.19 1.08 Invention 102 B-4 (12) -0.25 -0.22 -0.18 1.23 1.22 1.15 Invention 102 B-5 (14) -0.30 -0.26 -0.22 1.20 1.22 1.13 Invention 102 B -6 (40) -0.22 -0.25 -0.19 1.20 1.15 1.14 Invention 102 B-7 (79) -0.10 -0.09 -0.09 1.05 1.09 1.02 Invention 102 B-8 (93) -0.05 -0.08 -0.10 1.08 1.06 1.03 Invention 102 B-9 (107) -0.14 -0.08 -0.05 1.16 1.12 1.12 Invention 102 B-10 (118) -0.29 -0.26 -0.22 1.19 1.10 1.14 Invention ────────────よ り From Table 1 By processing a sample containing a tabular high silver chloride emulsion using a color developing solution containing a tetrahydroquinoline-based color developing agent as a compound of the present invention,
It can be seen that the sensitivity is improved and the gradation is improved.

Example 2 A sample 102 was cut into a width of 35 mm, and a Macbeth color checker was photographed using three samples under appropriate exposure conditions. Processing B-1, processing B-3, and processing B-7 were performed on these samples, respectively, and the obtained 3
A sample prepared by printing using a kind of developed negative film was subjected to a sensory evaluation of color reproducibility. As a result, it was found that a print prepared from a negative film obtained by performing a treatment using the compound of the present invention gave a more preferable image.

(Example 3) Sample 103 was prepared in exactly the same manner as in Sample 102 except that the high silver chloride tabular emulsion E of the fourth, fifth and sixth layers was changed to silver iodobromide tabular emulsion A with an equal silver amount. did. In Sample 102, the eighth layer of high silver chloride tabular emulsion F was replaced with silver iodobromide tabular emulsion B, and the ninth and tenth layers of high silver chloride tabular emulsion G were used.
Was changed to silver iodobromide tabular emulsion C in the same manner except that Sample 104 was prepared. Sample 102
Sample 105 was prepared in exactly the same manner except that high silver chloride tabular emulsion H of the twelfth and thirteenth layers was changed to silver iodobromide tabular emulsion D with an equal silver amount. Sample 10 prepared in this way
Processing B-8 of Example 2 was performed on 3, 104, and 105. Table 2 shows the results.

[0178]

[Table 2] 試 料 Sample processing Color development Sensitivity difference Gradation ratio ΔS (Y) ΔS (M) ΔS (C) r (Y) r (M) r (C) ────────────────────────── ────────── 102 B-8 (93) -0.05 -0.08 -0.10 1.08 1.06 1.03 Invention 103 B-8 (93) -0.09 -0.06 -0.83 1.09 1.10 0.54 Compare 104 B-8 ( 93) -0.06 -0.80 -0.11 1.12 0.61 1.09 Comparison 105 B-8 (93) -0.78 -0.08 -0.13 0.65 1.11 1.05 Comparison ───────────────────── ───────────────

The above results show that when any of the photosensitive layers contains no high silver chloride tabular emulsion, good characteristics regarding sensitivity and gradation cannot be obtained even in the processing method of the present invention.

Claims (1)

[Claims] 1. A support comprising at least one blue-sensitive layer, one green-sensitive layer and one red-sensitive layer on a support, and at least one non-photosensitive layer. The sum of the projected areas of the tabular silver halide grains having an aspect ratio of 2 or more accounts for 50% or more of the total projected area of the silver halide grains, and the silver chloride content is 60 to 100 mol%. A silver halide photographic light-sensitive material containing silver halide is subjected to color development processing using a processing solution containing at least one tetrahydroquinoline-based color developing agent represented by the following general formula (D). For processing silver halide color photographic light-sensitive materials. Embedded image 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 pair is a substituent. R ₇ represents an alkyl group, an aryl group or a heterocyclic group. R ₈ represents a substituent. m is 0
Represents an integer from to 3.