JPH09311421A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce silver stains of staining an automatic developing machine and photographic sensitive materials without affecting photographic performances even in the case of processing with low replenishment by using a developer containing specified compounds. SOLUTION: The developer comprises one kind of compound represented by formula I and one kind of the compound represented by formula II and the like, and in formulae I and II, each of R1 -R3 is an H or halogen atom or a substituent combining through a carbon atom or the like with a ring and at least one of them is a mercapto group; the compound of formula I may from a bis-type structure obtained by combining 2 radical groups each having a triazine ring free from one H atom from a optional C atom constituting the ring; each of R4 and R5 is, independently, the same as R1 -R<3> but each is not necessary to be a mercapto group; and M is an H atom or a cation, thus permitting an extremely good effect for preventing silver stains to be obtained without affecting any photographic performance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material or a light-sensitive material). More specifically, in the development processing of general-purpose black-and-white photographic light-sensitive materials, printing black-and-white photographic light-sensitive materials, medical and industrial X-ray black-and-white photographic light-sensitive materials, they are attached or deposited on a photosensitive material, a developing tank of an automatic processor, or a roller. The present invention relates to a method of reducing silver stains (also referred to as silver sludge) to be used and facilitating daily maintenance of appliances and machines.

[0002]

2. Description of the Related Art Generally, in the development processing of photosensitive materials,
From the viewpoints of speed, simplicity, and handling, an automatic developing machine (hereinafter referred to as an automatic developing machine) is often used.
In recent years, the demand for low replenishment and speeding up of development processing has been increasing, but to meet these demands,
One means is to increase the activity of the developer. In the processing of black-and-white photosensitive materials, the activity can be increased by increasing the concentration of the developing agent, but the deterioration due to air oxidation is remarkable.
Also, reducing the thickness of the photosensitive material (for example, the protective layer) is effective for rapid processing.

[0003] By the way, the use of a sulfite to prevent the deterioration of a developer has been known for a long time. However, since it has a dissolving action of silver halide, silver is eluted from the photosensitive material as a silver sulfite complex into the developer. Would. The silver complex is reduced in the developing solution and gradually adheres and accumulates on the developing tank and the roller. This is referred to as silver stain or silver sludge, which adheres to the photographic material to be processed, thereby contaminating the image or contaminating the self-developing machine itself. Therefore, it is necessary to periodically clean and maintain the equipment.

As described in JP-A-56-24347, a method for reducing such silver stain is to reduce silver ions eluted in a developer and / or to reduce silver ions to silver. There is known a method of adding a compound which suppresses the compound. However, since the time during which the reduction is suppressed is not sufficient, particularly when the replenishment amount is reduced, all of the developing solution in the developing tank is partially reduced until it is replaced with a new solution to be replenished. , Sufficient silver stain prevention effect cannot be obtained. Further, by increasing the addition amount of these compounds, the elution amount of silver ions can be reduced and the reduction suppression ability can be improved, but the photographic properties are greatly affected.

On the other hand, mercaptotriazines disclosed in Japanese Patent Application Laid-Open No. 3-282457 are known as compounds having a small effect on photographic properties and an excellent ability to suppress silver elution. Because of the large amount of metal that is carried out, it is not possible to maintain a sufficient concentration for suppressing silver elution, especially in the case of low replenishment amount treatment, and it is not possible to sufficiently suppress silver elution in running equilibrium, as well as yellow There is a problem that a soluble silver salt is formed and precipitates on the bottom of the developing tank. This can also be solved by increasing the addition amount as in the case of the above-mentioned compound, but it was unfortunately found that a yellow stain is generated in the light-sensitive material. It is considered that this is because the sparingly soluble silver salt was generated in the sensitive material and could not be completely eluted from the sensitive material.

On the other hand, as a result of the research conducted by the present inventors, surprisingly, at least one compound of the general formula (1) and at least one of the compounds of the general formulas (2) and (3) of the present invention were used. It has been found that the combined use of one kind enables a sufficient silver elution suppressing ability to be obtained with a smaller addition amount. Moreover,
It has been found that this effect has superadditivity, and that it exhibits a further excellent silver elution inhibiting ability as compared with the simple addition of the silver elution inhibiting ability of each compound.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a processing method for reducing silver stains that contaminate an automatic developing machine and a photosensitive material without affecting the photographic properties, even in a low replenishing process. It is in.

[0008]

The above object has been attained by the following methods (1) and (2). (1) In a method of developing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer,
Halogen characterized by using a developing solution containing at least one compound represented by the general formula (1) and at least one compound represented by the general formula (2) or (3). Processing method of silver halide photographic light-sensitive material.

[0009]

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In the general formula (1), R _{1 to} R ₃ represent a hydrogen atom, a halogen atom or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, and at least one is a mercapto group. is there. Further, two kinds of radicals obtained by removing one arbitrary hydrogen atom of carbon forming a triazine ring may be combined to form a bis type structure.

[0011]

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In the general formula (2), R ₄ and R ₅ may be the same or different and represent the same groups as R _{1 to} R _{3 in} the general formula (1). However, it does not necessarily have to be a mercapto group. M is a hydrogen atom or a cation.

[0013]

[Chemical 6]

In the general formula (3), Z is a nonmetallic atomic group or at least one O atom necessary for forming a 5-membered heterocycle having a total nitrogen number of 1 or 3 in cooperation with C and N, and / or Alternatively, it represents a non-metal atomic group necessary for forming a 5-membered heterocycle in cooperation with S atom and C and N. Further, it may be condensed with a hydrocarbon ring or a hetero ring. M is a hydrogen atom or a cation.

(2) The replenishing amount of the developer of (1) is 330 ml /
A method of processing a silver halide photographic light-sensitive material, which is characterized by being m ² or less.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the general formula (1) is added in an amount of 0.05 to 1 mmol, preferably 0.1
The amount of the compound of the general formula (2) or (3) added is 0.05 to 1.5 mmol, preferably 0.1 to 1.2 mmol, and the compound of the general formula (1) and the general formula (2) or ( The addition amount ratio of the compound of 3) is arbitrary.

Next, the compound of the general formula (1) will be described in detail. In the formula, R _{1 to} R ₃ represent a hydrogen atom, a halogen atom or a group bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, and at least one of these groups is a mercapto group. It may be condensed with a hydrocarbon ring or a hetero ring. Further, a radical 2 in which any hydrogen atom of carbon atoms forming a 6-membered ring is removed.
The seeds may combine to form a bis type structure.

The group bonded by the carbon atoms of R _{1 to} R ₃ includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carboxyl group and a cyano group. When the heterocyclic group is bound by an oxygen atom, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, or a sulfonyloxy group is bound by a nitrogen atom and is acylamino. Group, amino group, alkylamino group, arylamino group, heterocyclic amino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, imide group, heterocyclic group, Mel bonded as a sulfur atom Script group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkoxysulfonyl group, an aryloxy sulfonyl group, a sulfonyl group, a sulfo group, and a sulfinyl group. These may be further substituted with the groups described as R _{1 to} R ₃ . If possible, two of R _{1 to} R ₃ may combine to form a ring.

The details of R _{1 to} R ₃ will be described.
The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, such as methyl, ethyl, isopropyl,
t-butyl, benzyl and cyclopentyl. The alkenyl group has 2 to 10 carbon atoms and includes, for example, vinyl, 1-propenyl, 1-hexenyl and styryl. The alkynyl group has 2 to 10 carbon atoms and includes, for example, ethynyl, 1-butynyl and phenylethynyl. The aryl group is an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 8 carbon atoms, for example, carbamoyl, N-ethylcarbamoyl,
It is N-phenylcarbamoyl. The alkoxycarbonyl group has 2 to 8 carbon atoms, such as methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 12 carbon atoms,
For example, phenoxycarbonyl. The acyl group has 1 to 8 carbon atoms, such as acetyl and benzoyl. As the heterocyclic group linked by a carbon atom on the ring, an oxygen atom, a nitrogen atom or a sulfur atom having 1 to 5 carbon atoms is 1
It is a 5- or 6-membered saturated or unsaturated heterocycle containing 1 or more, and the number of heteroatoms constituting the ring and the number of elements may be one or more, for example, 2-furyl, 2
-Thienyl, 2-pyridyl, 2-imidazolyl.

The alkoxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxy and 2-
Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 12 carbon atoms and includes, for example, phenoxy, p-methoxyphenoxy, m-
(3-hydroxypropionamide) phenoxy. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and a hetero atom constituting the ring. And the number of elements may be one or more, for example, 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, 2
-Pyridyloxy. The acyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has 1 to 8 carbon atoms, such as methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 10 carbon atoms,
It preferably has 1 to 6 carbon atoms, such as acetylamino and benzoylamino. The alkylamino group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms,
For example, N, N-dimethylamino, N- (2-hydroxyethyl) amino, N- (3-dimethylaminopropyl)
It is Amino. Arylamino group has 6 to 1 carbon atoms
0, for example, anilino and N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and a hetero atom constituting the ring. The number and the kind of element may be one or plural, and examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino, and 4-pyridylamino. The ureido group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
10 to 10, preferably 0 to 5 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and is, for example, methoxycarbonylamino. The aryloxycarbonylamino group has 7 to 12 carbon atoms, such as phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The sulfonamide group has 1 to 10 carbon atoms, preferably 1 carbon atom.
To 6, for example, methanesulfonamide and p-toluenesulfonamide. The imide group has 4 carbon atoms
And N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocyclic ring composed of a nitrogen atom and at least one of a carbon atom, an oxygen atom or a sulfur atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 10 carbon atoms,
Preferably, it has 1 to 5 carbon atoms, such as methylthio,
It is 2-carboxyethylthio. The arylthio group has 6 to 12 carbon atoms, for example, phenylthio, 2
-Carboxyphenylthio. The heterocyclic thio group is a 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and a hetero atom constituting the ring. The number and the kind of element may be one or plural, and examples thereof include 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms
0, preferably those having 0 to 6 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsfamoyl. Alkoxysulfonyl group has 1 to 1 carbon atoms
0, preferably having 1 to 6 carbon atoms, for example, methoxysulfonyl. The aryloxysulfonyl group has 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.

The mercapto group is represented by -SM, and M is a hydrogen atom or a cation. Examples of the cation include sodium, potassium, lithium, calcium, ammonium, tetrabutylammonium and triethylammonium. M is preferably a hydrogen atom, sodium, potassium or ammonium.

R _{1 to} R ₃ are preferably hydrogen atoms,
Mercapto group, alkyl group, aryl group, carbamoyl group, acyl group, cyano group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, sulfonamide group, alkylthio group, arylthio group, Sulfamoyl group, a sulfonyl group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, a ureido group, an alkylthio group, and most preferably a hydrogen atom, an alkyl group, an alkoxy group, An amino group and an alkylthio group.

As the linking group for forming the bis type structure, a divalent linking group (alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group and -O-, -S- , -NH-, -CO-, -SO
_2- and the like, which are linked by a group consisting of a single or a combination thereof.

Examples of the alkylene group include ethylene,
Trimethylene, pentamethylene, propylene, 2-butene-1,4-yl, 2-butene-1,4-yl, p-xylylene. The alkenylene group is, for example, ethyn-1,2-yl. The alkynylene group is ethyn-1,2-yl. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. As the linking group, an alkylene group, -NH (alkylene) NH- group, -O (alkylene) O- group, -S (alkylene) S- group, -NH
(Alkylene) CONH (Alkylene) NH- group, -N
The H (alkylene) O (alkylene) NH- group is preferable, and the -NH (alkylene) NH- group and the -O (alkylene) O- group are more preferable.

Next, the general formula (2) will be described.
R ₄ and R ₅ may be the same or different and represent the same groups as R _{1 to} R _{3 in} the general formula (1). However,
R ₄ and R ₅ do not necessarily have to be mercapto groups.

Next, the general formula (3) will be described. In the formula, Z is a non-metallic atomic group or at least one O atom and / or S atom necessary for forming a 5-membered heterocycle having a total nitrogen number of 1 or 3 or more together with C and N, C, N
Represents a non-metal atomic group necessary for forming a 5-membered heterocyclic ring together with. This 5-membered ring may have a substituent bonded to the ring by a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. This 5-membered ring may be further condensed with a hydrocarbon ring or a heterocycle, and examples thereof include oxazole, thiazole, triazole, thiadiazole, oxadiazole, indazole, benzoxazole, benzothiazole, pyrazolotriazole,
Examples thereof include pyrrolotriazole. The 5-membered nitrogen-containing aromatic heterocycle is preferably triazole, thiadiazole, oxadiazole, benzoxazole, benzothiazole, pyrazolotriazole or pyrrolotriazole, more preferably triazole, thiadiazole or oxadiazole, most preferably Is triazole.

The substituent of the 5-membered ring of the general formula (3) will be described. This substituent is a halogen atom, or a carbon atom,
It is a group bonded to a ring by an oxygen atom, a nitrogen atom, or a sulfur atom. As the group bonded by a carbon atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carboxyl group, a cyano group or a heterocyclic group is an oxygen atom. A hydroxy group as a bond,
An alkoxy group, an aryloxy group, a heterocyclic oxy group,
The acyloxy group, the carbamoyloxy group, and the sulfonyloxy group which are bonded to each other by a nitrogen atom include an acylamino group, an amino group, an alkylamino group and an arylamino group,
A heterocyclic amino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, an imide group, and a heterocyclic group are bonded with a sulfur atom as-(SM).
_n group (M is H or cation; n is 0, 1 or 2), alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfonyl group, sulfo group, sulfinyl group Can be mentioned. These may be further substituted. There may be a plurality of substituents, and if possible, two substituents may combine to form a ring.

The substituent of the general formula (3) will be described in more detail. The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group has 1 carbon atom
-10, preferably a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, and examples thereof include methyl, ethyl, isopropyl, t-butyl, benzyl and cyclopentyl. The alkenyl group has 2 to 10 carbon atoms, and examples thereof include vinyl, 1-propenyl, 1-hexetyl and styryl. The alkynyl group has 2 to 10 carbon atoms.
And examples thereof include ethynyl, 1-butynyl and phenylethynyl. Aryl group has 6 to 1 carbon atoms
An aryl group of 0, such as phenyl, naphthyl, p-methoxyphenyl.

The carbamoyl group has 1 to 8 carbon atoms, and includes, for example, carbamoyl, N-ethylcarbamoyl,
It is N-phenylcarbamoyl. The alkoxycarbonyl group has 2 to 8 carbon atoms, such as methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 12 carbon atoms,
For example, phenoxycarbonyl. The acyl group has 1 to 8 carbon atoms, such as acetyl and benzoyl. As the heterocyclic group linked by a carbon atom on the ring, an oxygen atom, a nitrogen atom or a sulfur atom having 1 to 5 carbon atoms is 1
It is a 5- or 6-membered saturated or unsaturated heterocycle containing 1 or more, and the number of heteroatoms constituting the ring and the number of elements may be one or more, for example, 2-furyl, 2
-Thienyl, 2-pyridyl, 2-imidazolyl.

The alkoxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxy and 2-
Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 12 carbon atoms and includes, for example, phenoxy, p-methoxyphenoxy, m-
(3-hydroxypropionamide) phenoxy. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and a hetero atom constituting the ring. And the number of elements may be one or more, for example, 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, 2
-Pyridyloxy. The acyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has 1 to 8 carbon atoms, such as methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 10 carbon atoms,
It preferably has 1 to 6 carbon atoms, such as acetylamino and benzoylamino. The alkylamino group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms,
For example, N, N-dimethylamino, N- (2-hydroxyethyl) amino, N- (3-dimethylaminopropyl)
It is Amino. Arylamino group has 6 to 1 carbon atoms
0, for example, anilino and N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and a hetero atom constituting the ring. The number and the kind of element may be one or plural, and examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino, and 4-pyridylamino. The ureido group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
10 to 10, preferably 0 to 5 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and is, for example, methoxycarbonylamino. The aryloxycarbonylamino group has 7 to 12 carbon atoms, such as phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The sulfonamide group has 1 to 10 carbon atoms, preferably 1 carbon atom.
To 6, for example, methanesulfonamide and p-toluenesulfonamide. The imide group has 4 carbon atoms
And N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocyclic ring composed of a nitrogen atom and at least one of a carbon atom, an oxygen atom or a sulfur atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 10 carbon atoms,
Preferably, it has 1 to 5 carbon atoms, such as methylthio,
It is 2-carboxyethylthio. The arylthio group has 6 to 12 carbon atoms, for example, phenylthio, 2
-Carboxyphenylthio. The heterocyclic thio group is a 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and a hetero atom constituting the ring. The number and the kind of element may be one or plural, and examples thereof include 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms.
0, preferably those having 0 to 6 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsfamoyl. Alkoxysulfonyl group has 1 to 1 carbon atoms
0, preferably having 1 to 6 carbon atoms, for example, methoxysulfonyl. The aryloxysulfonyl group has 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.

The substituent of the general formula (3) is preferably
Hydrogen atom, alkyl group, aryl group, carbamoyl group,
Acyl group, cyano group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, sulfonamide group,-(SM) _n group,
Alkylthio group, arylthio group, sulfamoyl group,
A sulfonyl group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group,
An acylamino group, an ureido group, an alkylthio group,
Most preferably a hydrogen atom, an alkyl group, an alkoxy group,
An amino group, a-(SM) _n group, and an alkylthio group.

The cation of M is, for example, sodium, potassium, lithium, calcium, ammonium, tetrabutylammonium or triethylammonium. M is preferably a hydrogen atom, sodium,
Potassium and ammonium. n is preferably 0 or 1. Specific examples of the compounds represented by the general formula (1), the general formula (2) and the general formula (3) in the present invention are shown below, but the invention is not limited thereto.

[0042]

[Chemical 7]

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

[Chemical 12]

[0048]

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The processing agents and processing methods such as the developing solution and the fixing solution in the present invention will be described below. Needless to say, the present invention is not limited to the following description and specific examples.

Any known method can be used for the development treatment of the present invention, and a known development processing solution can be used.

The developing solution used in the present invention (hereinafter, both the developing starting solution and the developing replenishing solution are collectively referred to as a developing solution).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonic acid salts, and may be used alone or in combination. Further, from the viewpoint of developing ability, a combination of a dihydroxybenzene or an ascorbic acid derivative with 1-phenyl-3-pyrazolidone or a combination of a dihydroxybenzene or an ascorbic acid derivative with a p-aminophenol is preferred. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred. Ascorbic acid derivative developing agents include ascorbic acid, isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferable from the viewpoint of material cost.

The developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention is 1-phenyl-3
-Pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone and others. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, etc. However, N-methyl-p-aminophenol is preferable among them.

The dihydroxybenzene type developing agent is usually 0.
It is preferably used in an amount of 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l to 0.5 mol / l. It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is usually 0.
It is preferably used in an amount of from 01 mol / l to 0.5 mol / l, more preferably from 0.05 mol / l to 0.3 mol / l. When a combination of an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or p-aminophenol is used, the ascorbic acid derivative may be used in an amount of 0.01 to 0.5 mol / l, and the 1-phenyl-3-pyrazolidone or p-aminophenol may be used. The aminophenols are preferably used in an amount of from 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention can contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259, JP-A-60-9
The sugars described in 3433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like, preferably carbonates , Boric acid is used. The amount of buffer, especially carbonate, used is preferably at least 0.1 mol / l, in particular from 0.2 to
It is 1.5 mol / liter.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. Sulfite is used in an amount of 0.2 mol / L or more, particularly 0.3 mol / L or more. However, if added in an excessive amount, it causes silver contamination in the developing solution.
It is desirable to use liters. Particularly preferably, 0.35 to
0.7 mole / liter. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Other additives to be used include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (eg, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound may be contained as an antifoggant or a black pepper (black pepper) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2- Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate sodium, 5-amino-1,3,4 -Thiadiazole-2-thiol,
Methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these additives is usually 0.01 to 10 mmol per liter of developer, more preferably 0.1 to 10 mmol.
~ 2 mmol.

Further, various kinds of organic,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As the aminopolycarboxylic acid, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, 1
, 2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and other JP-A-52-25632, 55-67747, and 57-1
02624 and compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acids described in US Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication No. 2227369, Research Disclosure Vol. 181, Item 18170 (1979).
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid.
Other examples include the compounds described in Research Disclosure 18170, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883, and JP-A-56-97347.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, 54-121127 and 55.
-4024, 55-4025, 55-126241, 55-65955, 55
-65956 and the aforementioned Research Disclosure 1817
0 and the like.

These organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of the developer.

Further, in addition to the compound of the present invention as a silver stain preventing agent in a developer, a pyrimidine having one or more mercapto groups (for example, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercapto). Pyrimidine,
5, 6-diamino-2, 4-dimercaptopyrimidine, 2, 4
, 6-trimercaptopyrimidine, etc., the same pyridine (for example, 2-mercaptopyridine, 2, 6-dimercaptopyridine, 3, 5-dimercaptopyridine, 2, 4, 6-trimercaptopyridine, JP-A-7-248587). Described compounds), the same pyrazine (for example, 2-mercaptopyrazine,
2, 6-dimercaptopyrazine, 2, 3-dimercaptopyrazine, 2, 3, 5-trimercaptopyrazine, etc., and the same pyridazine (for example, 3-mercaptopyridazine, 3, 4-dimercaptopyridazine, 3, 5-dimer) (Mercaptopyridazine, 3, 4, 6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177, polyoxyalkylphosphonates described in US Pat. No. 5457011, and the like can be used. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is 1 liter per 1 liter of developer.
0.05 to 10 mmol is preferable, and 0.1 to 5 mmol is more preferable. In addition, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color toning agent, a surfactant, a defoaming agent, a hardener and the like may be contained.

The pH of the developer is preferably 9.0 to 12.0, particularly preferably 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As the cation of the developing solution, potassium ion is preferred as compared with sodium ion because it does not suppress development and the occurrence of jagged edges around the blackened portion called fringes is preferable. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However, in the fixing solution, potassium ions inhibit fixing to the same extent as silver ions. Therefore, if the potassium ion concentration in the developing solution is high, the potassium ion concentration in the fixing solution is increased because the developing solution is brought in by the photosensitive material. It becomes high and is not preferable. From the above, the molar ratio of potassium ion to sodium ion in the developer is 20:80.
It is preferably between ˜80: 20. The ratio of potassium ion and sodium ion is pH buffer, pH adjuster,
Counter cations such as preservatives and chelating agents can be optionally adjusted within the above range.

The replenishment amount of the developing solution is 39 per 1 m ² of the light-sensitive material.
It is 0 ml or less, preferably 330 to 30 ml, and most preferably 180 to 120 ml. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration from the start solution.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent to be used can be changed as appropriate, but is generally from about 0.7 to about
It is 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are used as an aluminum ion concentration of 0.01 to 0.15 mol /
It is preferably contained in liters. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

If desired, a preservative (eg, sulfite, bisulfite, metabisulfite, etc.) may be used in the fixing treatment agent in an amount of 0.015
Mol / l or more, preferably 0.02 mol / l ~
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / l to 1 mol / l, preferably 0.2 mol / l to 0.7 mol / l of phosphoric acid, succinic acid, adipic acid, etc., and compounds having aluminum stabilizing ability or water softening ability (for example, gluconic acid, iminodi Acetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediamine Acetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides, boric acid, etc.
1 mol / l to 0.5 mol / l, preferably 0.
005 mol / l to 0.3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene-based surfactants, and amphoteric surfactants described in JP-A-57-6840. Can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754 and 58-122535.
58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,216,459, JP-A-64-4739, JP-A-1-4739, JP-A-1-4739.
159645 and the mercapto compounds described in 3-101728,
The mesoionic compound described in 4-170539 and a thiocyanate can be included.

The pH of the fixing solution in the present invention is 4.0 or more, preferably 4.5 to 6.0. The pH of the fixing solution is raised by the processing mixed with the developing solution. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixing solution, and 7.0 or less, preferably 6.7 or less for the non-hardened fixing solution.

The replenishing amount of the fixing solution is 50 per 1 m ² of the light-sensitive material.
0 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml. The replenishing solution may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration as the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing processing agent in the present invention is a liquid agent, it is preferably stored in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Furthermore, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Even when the developing treatment agent and the fixing treatment agent in the present invention are solid, the same results as in the case of the liquid agent can be obtained. The solid treatment agent will be described below. The solid preparation in the present invention may be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating aids can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrene sulfonic acid and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3
You can refer to the 13th line.

In the case of forming a plurality of layers, the components which do not react even when contacted may be sandwiched between the components which react with each other and processed into tablets or briquettes, or the components of known form may be used. It may be packaged in the same layer structure. These methods are described in, for example, JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g / cm.
³ , particularly preferably 1.0 to 5.0 g / cm ³ for tablets, and 0.5 to 1.5 g / cm ^{3 for} granules.

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-
32837, 4-78848, 5-93991, JP-A-4-85533,
4-85534, 4-85535, 5-134362, 5-97070, 5-
204098, 5-224361, 6-138604, 6-138605, Japanese Patent Application
7-89123 etc. can be referred to.

More specifically, rolling granulation method, extrusion granulation method, compression granulation method, crushing granulation method, stirring granulation method, spray drying method, melt coagulation method, briquetting method, roller compaction method. The Ting method or the like can be used.

The solid agent of the present invention can be adjusted in solubility by changing the surface condition (smoothness, porosity, etc.) or partial thickness, or by forming a hollow donut shape.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material of the solid agent is preferably a material having low oxygen and water permeability, and the packaging material may have a known shape such as a bag shape, a tubular shape or a box shape. Also, JP-A-6-242585-
6-242588, 6-247432, 6-247448, Japanese Patent Application 5-30664
Also, it is preferable to make it a foldable shape as disclosed in JP-A-7-5664 and JP-A-7-5666 to 7-5669, in order to reduce the storage space of the waste packaging material. These packaging materials
A screw cap, a pull top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and there is no particular limitation. Further, in terms of environmental protection, it is preferable to recycle or reuse the waste packaging material.

The method of dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and known methods can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function,
A method of dissolving with a dissolving apparatus having a dissolving portion and a portion for storing a completed solution as described in 7-235499 and replenishing from the stock portion, JP-A-5-119454, JP-A-6-19102,
A method of dissolving and replenishing by introducing a processing agent into the circulating system of an automatic developing machine as described in 7-261357, and inputting a processing agent according to the processing of the photosensitive material with an automatic developing machine having a built-in dissolving tank. Although there is a dissolving method and the like, any other known method can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferred from an environmental point of view. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method disclosed in JP-A-6-19102
And 6-95331.

The light-sensitive material which has been developed and fixed is then washed with water or stabilized (hereinafter, referred to as washing including stabilizing unless otherwise specified. The liquid used for these is water or water for washing). That.). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. The amount of replenishment is generally but about 17 liters to about eight liter photosensitive material 1 m ^2, can also be carried out in less replenishing rate. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method for reducing the replenishing amount of water washing, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time, and the replenishing amount of water washing is preferably 200 to 50 ml per 1 m ² of the light-sensitive material. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Furthermore, a means for preventing scales may be added to the washing step by the method of the present invention. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-
Mercaptopyridine-N-oxide, etc.)
They may be used alone or in combination. As a method of energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, JP-A-4-18
980 or the like can be used.

In addition, a known water-soluble surfactant or defoaming agent may be added to prevent unevenness of water bubbles and stain transfer. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a washing system to prevent contamination by a dye eluted from the light-sensitive material.

As described in JP-A-60-235133, a part or all of the overflow liquid from the water washing step can be mixed and used in a processing liquid having fixing ability. In addition, microbial treatment (for example, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain a biochemical oxygen demand. Water (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and examples thereof include JP-A-2-201357 and JP-A-2-132435.
A bath containing a compound described in JP-A-1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents,
Hardening agents, fungicides, sunscreens, alkanolamines and surfactants can also be added.

Additives such as antifungal agents and stabilizers to be added to the washing and stabilizing baths may be solid agents like the above-mentioned developing and fixing processing agents.

Waste liquids of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention are preferably incinerated. These waste liquids are described in, for example, Japanese Patent Publication No. 7-83867, US
It is also possible to dispose it after concentrating it into a liquid or solidifying it with a concentrating device as described in O.

When the replenishment amount of the processing agent is reduced, it is preferable to reduce the opening area of the processing tank to prevent the evaporation of liquid and the oxidation of air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. Further, a rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, dry to dry 25 to
160 seconds is preferred, the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is preferably 25 to 50 ° C.
30-40 ° C is preferred. Washing temperature and time are 0-50 ℃
And preferably 40 seconds or less. According to the method of the present invention, development,
The fixed and washed photosensitive material may be dried by squeezing washing water, that is, passing through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known method can be used for the drying method and is not particularly limited.
Heat roller drying and drying by far-infrared rays as disclosed in 4-15534, 5-2256 and 5-289294 may be used, and a plurality of methods may be used in combination.

Next, the emulsion for the light-sensitive material for scanners and line images in the present invention will be described. The silver halide emulsion according to the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide and silver iodobromide, but the silver chloride content is 30 mol% or more. Is preferable, and 50 mol% or more is more preferable. The content of silver iodide is preferably at most 5 mol%, more preferably at most 2 mol%.

The shape of the silver halide grains may be cubic, tetradecahedron, octahedron, amorphous, or plate-like, but cubic or plate-like is preferred.

The photographic emulsion used in the present invention is P. Glafki.
des by Chimie et Physique Photographique (Paul Mo
Published by ntel, 1967), Photographi by GFDufin
c Emulsion Chemistry (The Focal Press, 1966
Year), Making and Coating Photo by VLZelikman et al
graphic Emulsion (The Focal Press, 1964)
It can be prepared using the method described in, for example.

That is, any of an acidic method and a neutral method may be used, and as a method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Is also good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent to be added varies depending on the type of the compound used, the intended grain size, and the halogen composition, but is preferably 2 × 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and it is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above paragraph to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
It is 1 μm to 0.4 μm.

The silver halide emulsion used in the present invention is
It may contain a metal belonging to Group VIII. In particular, the photosensitive material suitable for high illuminance exposure such as scanner exposure and the photosensitive material for line drawing preferably contain a rhodium compound, an iridium compound, a ruthenium compound or the like in order to achieve high contrast and low fog. Further, it is preferable to contain an iron compound for higher sensitivity. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamine rhodium ( III) Complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of a rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg, KCl, NaCl,
KBr, NaBr, etc.). Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.
Examples of the iridium compound used in the present invention include hexachloroiridium, hexabromoiridium, and hexaammineiridium. Examples of the ruthenium compound used in the present invention include hexachlororuthenium and pentachloronitrosylruthenium. As the iron compound used in the present invention, hexacyanoiron (II)
And potassium ferrous thiocyanate.

The addition amount of these compounds is 1 × 10 ^{-8 to} 5 × 10 ^-6 mol, preferably 5 × 10 ^-8 to 1 × 10 ^-6 mol, per 1 mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. .

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually the sulfur sensitization.
Add a yellow sensitizer and keep the emulsion at a high temperature of 40 ℃ or more
It is performed by stirring for a while. Public sulfur sensitizer
Known compounds can be used, eg in gelatin
In addition to the sulfur compounds contained in, various sulfur compounds,
For example, thiosulfates, thioureas, thiazoles, rhodani
And the like can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. Addition of sulfur sensitizer
The amount depends on the pH, temperature and the size of silver halide grains during chemical ripening.
Changes under various conditions such as
10 per mole ^-7-10^-2Mole, more preferably
10^-Five-10^-3Is a mole.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compound represented by (IX).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and the compounds described in Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol per mol can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added according to the method disclosed in European Patent Publication (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, those having different crystal habits, and those having different conditions of chemical sensitization) may be used in combination.

Next, the emulsion of the reversal light-sensitive material in the present invention will be described. The silver halide emulsion of the present invention comprises Ir,
Contains at least one heavy metal selected from Ru, Rh, Re, and Cr. Preferred as these heavy metals are metal coordination complexes, and hexacoordination complexes represented by the following general formula. [M (NY) m L _6-m ] n (In the formula, M is a heavy metal selected from Ir, Ru, Rh, Re and Cr. L is a bridging ligand. Y is oxygen or sulfur. M = 0, 1, 2 and n = 0, -1,-.
2 and -3. ) Preferred examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyan Nate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands. Specific examples of the metal coordination complex are shown below. 1. [Rh (H ₂ O) Cl ₅ ] ^-2 . [RuCl ₆ ] ^-3 3. [Ru (NO) Cl _5] ^-2 4. [RhCl ₆ ] ^-3 5. [Ru (H ₂ 0) Cl ₅ ] ⁻² 6. [Ru (NO) (H ₂ O) Cl ₄ ] ⁻¹ 7. [Ru ₂ Cl ₁₀ O] ^-2 8. [Re (NO) Cl ₅ ] ^-2 9. [Ir (NO) Cl _5] ^-2 10. [Ir (H ₂ 0) Cl _5] ^-2 11. (Re (H ₂ 0) Cl ₅ ) ^-2 12. (RhBr ₆ ) ^-3 13. (ReCl ₆ ) ^-3 14. (IrCl ₆ ) ^-3 15. (Re (NS) Cl ₄ (SeCN)) ^{- 2} 16. [Cr (CN) ₆ ] ^-3

The above metal complex can be added to the silver halide during grain preparation. The content of the heavy metal in the silver halide grains of the present invention is from 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide. Preferably 10 ^{-6 to} 3 × 10 ^-4 mol, more preferably 1 × 10
^-6 mol to 2 × 10 ^-4 mol. Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grain is not particularly limited, but it is preferable that the heavy metal is more present outside the grain.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is silver chlorobromide, silver chloroiodobromide or silver chloride in which 95 mol% or more, particularly 99 mol% or more, is silver chloride. . Most preferred is silver chloride. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention has an average grain size of 0.20.
μm or less. In particular, it is preferably from 0.08 to 0.16 μm. If the particle size exceeds 0.2 μ, γ will decrease, and Dmax of the practical technique will decrease. In the present invention, the reaction temperature is 5 as a mixing condition for adjusting the silver halide grains.
At a temperature of 0 ° C. or less, preferably 40 ° C. or less, a silver potential of 70 mV or more, preferably 300 mV to 500 mV, or 5,6-cyclopentane-4-hydroxy-1,3 under a condition of sufficiently high stirring speed for uniform mixing. 80 mV in the presence of a stabilizer such as 3,3a, 7-tetrazaindene
Good results can be obtained by adjusting the voltage to 120 mV. The particle size distribution is basically not limited, but it is preferably monodisperse. Here, the monodispersion means that at least 95% of the weight or the number of particles is ± 4 of the average particle size.
It is composed of particle groups having a size within 0%, more preferably within ± 20%. The silver halide grain of the present invention preferably has a regular crystal such as a cube and an octahedron, and a cube is particularly preferable.

In the present invention, the grain formation of the silver halide emulsion is preferably carried out under acidic conditions. This is effective for minimizing fog in the subsequent chemical sensitization by the gold-sulfur sensitizer. The acidic condition is pH
4.0 or less, and preferably from pH 3.0 to pH 1.5.
It is.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is chemically sensitized after the grain formation, that is, gold sulfur sensitization, by the gold sensitizer and the sulfur sensitizer. As the above gold sensitizer, 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.
Known sulfur sensitizers can be used. For example, thiosulfates, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
And rhodanine. Other US Patent No. 1,5
No. 74,944, No. 2,410,689, No. 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The addition amount of the sulfur sensitizer varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but is not less than 1 × 10 ⁻⁷ mol per mol of silver halide. 5x
It is preferably 10 ^-4 mol or less. Chemical sensitization with these sensitizers is performed by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain period of time after the addition of the sensitizer.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is more preferably subjected to gold sulfur selenium sensitization in combination with a selenium sensitizer. As the selenium sensitizer preferably used in the present invention, a selenium compound disclosed in a conventionally known patent can be used. That is, it 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 40 ° C. or higher for a certain time. As an unstable selenium compound,
No. 15748, Japanese Patent Publication No. 43-13489,
No. 25832, Japanese Patent Application Laid-Open No. 4-109240, Japanese Patent Application No. Hei 3-109240.
It is preferable to use the compounds described in No. 92929 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropions, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. can give. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. 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 advantageously used. Non-labile selenium compounds used in the present invention include JP-B-46-4553,
JP-B-52-34492 and JP-B-52-3449
The compound described in No. 1 is used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Preferably, Japanese Patent Application No. Hei 6-2501
Compound Examples I-1 to I-20 and II-21 described in No. 56
To II-43.

The addition amount of the selenium sensitizer varies over a considerable range under various conditions such as pH, temperature and size of silver halide grains, but it is 1 × 10 ⁻ per mol of silver halide. ^It is preferably ⁷ mol or more and 5 × 10 ⁻⁴ mol or less.

In addition to these sensitizers, a noble metal such as platinum or palladium, a first tin salt, an amine, a reduction sensitizer such as formamidinesulfinic acid or a silane compound may be used in combination. The silver halide grains of the present invention are preferably added with a thiosulfonic acid compound represented by the following general formulas (A), (B) and (C) in the step of grain formation and / or gold sulfur sensitization. As a result, an emulsion having a lower fog can be obtained. (A) in _{R-SO 2 S-M (} B) R-SO 2 S-R1 (C) R-SO 2 S-Lm-SSO 2 -R2 formula, R, R1, R2, which may be the same or different , An aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m represents 0 or 1
It is. The compounds of the general formulas (A) to (C) are
Or a polymer containing a divalent group derived from the structure shown in (C) as a repeating unit.

The amount of the thiosulfonic acid compound added varies over a considerable range under various conditions such as pH, temperature and size of silver halide grains, but it is 1 × 10 ⁻ per mol of silver halide. ^It is preferably ⁷ mol or more and 5 × 10 ^-2 mol or less.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and those described in the following sections can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5; Specifically, compounds (III) -1 to 25 described in the publication.

A compound represented by the general formula (I) described in JP-A-1-118832, which has substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds 1-26.

Antifoggants described in JP-A-2-103536, page 17, lower right line, line 17 to page 18, upper right line, fourth line.

Polymer latices described in JP-A-2-103536, page 18, lower left line 12 to lower left line 20 of the same page. General formula (I) described in Japanese Patent Application No. 8-13592.
A polymer latex having an active methylene group represented by the formula:
6. Polymer latex having a core / shell structure described in Japanese Patent Application No. 8-13592, specifically, compounds P-1 to P-55 described in the specification.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line, line 15 to page 19, upper right line, line 15.

Hardeners described in JP-A-2-103536, page 18, upper right, line 5 to upper right, line 17 of the same page.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right line, line 6 to page 19, upper left line, first line.

JP-A-2-18542, page 2, lower left 1
Conductive substances from the third line to the seventh line on the upper right of page 3 of the publication. Specifically, the metal oxides described in page 2, lower right line, page 2 to lower right line, line 10 of the same publication, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication. .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right line, line 1 to upper right line, page 18;

Solid dispersion dyes represented by formula (FA), formula (FA1), formula (FA2) and formula (FA3) described in Japanese Patent Application No. 7-350753. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
Nos. (II-2) to (II-24) described in JP-A-7-1521
No. 12, (III-5) to (III-18), JP-A-7-15
(IV-2) to (IV-7) described in No. 2112.

Solid disperse dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773.

JP-A-2-12236, page 9, upper right corner 7
The surfactant described in the third line from the line on the lower right side of the same page. JP-A-2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds VI-1 to VI-15 described in the publication.

The following nucleation accelerators such as amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. JP-A-7-77783, page 48, line 2 to
Compounds described in line 37, specifically, compounds A-1) to A-73) described on pages 49 to 58. JP-A-7-843
(Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. General formula (1) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19 described
2-1 to 2-22, 3-1 to 3-3
6, compound 4-1 to 4-5, 5-1 to 5-4
1 compound, 6-1 to 6-58 compound and 7-1 to
Compounds 7-38.

Hydrazine derivatives shown below. Japanese Patent Application Hei 6
No. 47961, a compound represented by the general formula (I), specifically, a compound represented by I-1 to I-53 described in the same specification. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082.
Compounds 1 to 38 on page 18. JP-A-6-2304
No. 97, compounds represented by the general formula (4), the general formula (5) and the general formula (6).
Compounds 4-1 to 4-10, 2 described on page 26.
Compounds 5-1 to 5-42 described on pages 8 to 36, and compounds 6-1 to 6-7 described on pages 39 and 40.
Compounds represented by general formulas (1) and (2) described in JP-A-6-289520.
Compounds 1-1) to 1-17) and 2 described on pages 7 to 9
-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936.
Compounds described on page 19 to page 19. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically compounds I-1 to I-38 described on pages 5 to 10 of the same; Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the publication. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the same publication. As described in Japanese Patent Application No. 7-191007,
A compound characterized by having an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. Particularly, compounds represented by the general formulas (A), (B) and ( C), compounds represented by formulas (D), (E) and (F), specifically, compounds N-1 to N-30 described in the same publication. Japanese Patent Application No. 7-19
Compounds represented by the general formula (1) described in 1007, specifically, compounds D-1 to D-55 described in the same publication.

Redox compounds described in JP-A-5-274816 which can release a development inhibitor by being oxidized. Preferably, the general formula (R-1) described in the publication,
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

JP-A-2-18542, page 3, lower right corner 1
The binder described in the second to 20th lines.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes for use in the present invention are described in, for example, RESEARCH DISCLOSURE Item 17643 IV-A (December 1978, p. 23) and Item 1831X (August 1979, p. 437) or cited in the literature. Have been. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate-making cameras can be advantageously selected.
For example, A) for an argon laser light source, (I) -1 to (I)-described in JP-A-60-162247.
No. 8, compound I-1 to I-28 described in JP-A-2-48653, compound I-1 to I-13 described in JP-A-4-330434, U.S. Pat.
No.331 to Example1 to Example
Compound No. 14; compounds Nos. 1 to 7 described in West German Patent 936,071; B) For helium-neon laser light source, I-1 to I described in JP-A-54-18726.
-38 compound, I- described in JP-A-6-75322.
Compounds from 1 to I-35 and JP-A-7-287338
Compounds I-1 to I-34 described in JP-A-55-39818 (C).
To 20, described in JP-A-62-284343.
To I-37 and the compounds of I-1 to I-34 described in JP-A-7-287338; and D) For the semiconductor laser light source, the compounds of I-1 to I-37 described in JP-A-59-191332. -12 compound, JP-A-60-8084
Compounds of I-1 to I-22 described in No. 1;
Compounds I-1 to I-29 described in JP-A-335342 and I-1 to I-29 described in JP-A-59-192242.
-18 compound, E) for tungsten and xenon light sources of a plate making camera, compounds (1) to (19) represented by general formula [I] described in JP-A-55-45015; No. 7-346193, I-1 to I-9
Compound 7 and 4 described in JP-A-6-242547.
A compound of -A to 4-S, a compound of 5-A to 5-Q,
Compounds such as 6-A to 6-T are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. 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. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section IV on page IV, or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242.

The sensitizing dyes used in the present invention may be used in combination of two or more kinds. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye by using a red-shifting compound and adding the solution into an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye for use in the present invention may be added to the silver halide emulsion of the present invention at any step in the preparation of emulsions which has heretofore been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the silver halide grain forming step and / or before the desalting, during the desilvering step and / or after the desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after the chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape, size, halogen composition, method and degree of chemical sensitization, type of antifoggant and the like of silver halide grains. 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester film such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

[0139]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

<Preparation of Photosensitive Material (1)> Preparation of Emulsion A 1-liquid water 1-liter gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2-liquid water 400 ml Silver nitrate 100g 3 liquid water 400ml Sodium chloride 27.1g Potassium bromide 21.0g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20ml Potassium hexachlorodium (III) (0.001% aqueous solution) 6ml

Liquids 2 and 3 were added simultaneously to liquid 1 kept at 42 ° C. and pH 4.5 for 15 minutes with stirring to form core particles. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate were added and chemically sensitized at 55 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 70 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion A having an average grain size of 0.25 μm was obtained. Preparation of Coated Sample Emulsion A was added with 3.8 × 10 ^-4 mol / mol Ag of sensitizing dye and subjected to spectral sensitization. Furthermore, KBr 3.4 × 10 ^-4 mol / mol Ag, compound 3.2 × 10 ^-4 mol / mol A
g, compound 8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0
× 10 ^-3 mol / mol Ag, compound 1.0 × 10 ^-4 mol / mol Ag, compound 6.0 × 10 ^-4 mol / mol A
g, 35% by weight of polyethyl acrylate latex with respect to gelatin, 20% by weight of colloidal silica having a particle size of 10 μm with respect to gelatin, and 4% with respect to gelatin.
was added to wt% of the compound, Ag3.7g / m ² on a polyester support was coated to a gelatin 1.6 g / m ^2. A protective layer upper layer and a protective layer lower layer having the following compositions were coated thereon, and a UL layer having the following composition was coated thereunder. Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent with an average of 3.5 μm 25 mg / m ² compound (gelatin dispersion) 20 mg / m ² Colloidal silica with a particle size of 10 to 20 μm 30 mg / m ² compound 5 mg / m ² dodecyl Sodium benzenesulfonate 20 mg / m ² compound 20 mg / m ² protective layer lower layer gelatin 0.5 g / m ² compound 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² compound 40 mg / m ² compound (10) 10 mg / m ²

The support has a back layer and a conductive layer having the following composition. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² polymethylmethacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² compound 120 mg / m ² conductive layer gelatin 0.1 g / m ² sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb ( 9/1 weight ratio, average particle size 0.25μ) 200 mg / m ²

<Preparation of Photosensitive Material (2)> Preparation of Emulsion B 1-liquid water 1-liter gelatin 20 g sodium chloride 2.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2-liquid water 400 ml Silver nitrate 100g 3 liquid water 400ml Sodium chloride 27.1g Potassium bromide 21.0g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20ml Potassium hexachlorodium (III) (0.001% aqueous solution) 7ml

To the 1st liquid kept at 40 ° C. and pH 4.5, the 2nd liquid and the 3rd liquid were added simultaneously with stirring for 15 minutes,
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

Thereafter, the flocculation is performed according to a conventional method.
The mixture was washed with water by the spin method and 40 g of gelatin was added. pH
5.7, pAg adjusted to 7.5, sodium thiosulfate
1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine
Selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate at 55 ° C
Chemically sensitized to obtain optimum sensitivity. As a stabilizer
4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene 100mg, phenoxy as preservative
Ethanol is added and finally contains 70 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion A having an average grain size of 0.23 μm was obtained.
Was. Preparation of coating sample Emulsion B: Sensitizing dye 2.0 × 10^-FourMol / mol Ag, increase
Sensitizing dye 7.0 × 10 ^-FourAdd mol / mol Ag to increase spectral
I gave a feeling. Furthermore, Kbr 3.4 × 10^-FourMol / mol A
g, compound 5.0 × 10^-FourMol / mol Ag, compound
8.0 x 10^-FourMol / mol Ag, hydroquinone 1.2
× 10^-2Mol / mol Ag, compound 1.8 × 10^-FourMo
Le / mol Ag, compound 3.5 × 10^-FourMol / mol A
g, and 30 wt% of polyethyl acetate based on gelatin.
15 wt% of acrylate latex and gelatin
4 for colloidal silica and gelatin with a particle size of 10 mμ
Add wt% compound to polyester support
Ag 3.4 g / m^Two, Gelatin 1.5g / m^TwoTo be
Applied. On top of this, a protective layer and a protective layer having the following composition
A lower layer was coated with a UL layer having the following composition below. Upper layer of protective layer Gelatin 0.3 g / m^Two An average of 3.5 μm silica matting agent 25 mg / m^Two Compound (gelatin dispersion) 20 mg / m^Two Colloidal silica having a particle size of 10 to 20 μm 30 mg / m^Two Compound 5mg / m^Two Sodium dodecylbenzene sulfonate 20mg / m^Two Compound 20mg / m^Two Lower layer of protective layer Gelatin 0.5g / m^Two Compound 15mg / m^Two 1,5-dihydroxy-2-benzaldoxime 10 mg / m^Two Polyethyl acrylate latex 250mg / m^Two UL layer gelatin 0.5g / m^Two Polyethyl acrylate latex 150mg / m^Two Compound 40mg / m^Two

The support has the same back layer and conductive layer as the photosensitive material (1). <Preparation of Photosensitive Material (3)> Preparation of Emulsion C 3 × 1 per mol of sodium chloride and silver kept at 38 ° C.
0 ^-5 mole of sodium benzenethiosulfonate, 5 × 1
0 ^-3 mole of 4-hydroxy-6-methyl-l, 3,3
a, 1.5 containing pH = 2.0 containing 7-tetrazaindene
% Gelatin aqueous solution, silver nitrate and 5 × 10
A sodium chloride aqueous solution containing ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ was simultaneously added by the double jet method at a potential of 95 mv for 3 minutes and 30 seconds to half the amount of silver of the final particles, and the particle diameter of the core particles was 0.1.
12 μm was prepared. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 5 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes, and a silver chloride cube having an average grain size of 0.13 μm was added. Particles were prepared. (Coefficient of variation: 12%) Thereafter, the resultant was washed with water by a flocculation method well known in the art to remove soluble salts, and then gelatin was added.
Compound (15) and phenoxyethanol as preservatives in silver 1
After adding 60 mg each per mole, pH 5.5, pAg = 7.
To 5 ×, and 4 × 10 ^-5 mol of chloroauric acid, 1 × 10 ^-5 mol of selenium compound (14) and 1 × 10 ⁵ mol per mol of silver.
^-5 mol of sodium thiosulfate was added, and the mixture was heated at 60 ° C for 60 minutes for chemical sensitization, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer to silver. 1 × 10 ⁻³ mol was added per mol (as final particles, pH = 5.7, pAg = 7.5, Ru = 5 × 10 5).
^This resulted in silver chloride containing ^-5 mol / Ag mol. )

<Preparation of Coating Sample> (Silver Halide Emulsion Layer) The following compound was added to Emulsion C to give a gelatin coating amount of 0.9 g on a support described below including an undercoat layer.
/ M ^2, the coating amount of silver coated with silver halide emulsion layer as a 2.75 g / m ^2. N-oleyl-N-methyltaurine sodium salt 19 mg / m ² Hydrazine derivative shown in Table 13 15 mg / m ² compound (16) 20 mg / m ² 3- (5-mercaptotetrazole) -sodium benzene sulfonate 11 mg / m ² compound (17) 13 mg / m ² ascorbic acid 1 mg / m ² compound (18) 15 mg / m ² compound (19) 70 mg / m ² acetic acid Amount at which the film surface pH becomes 5.2 to 6.0 Compound (20) 950 mg / m ² ribolane-1400 (manufactured by Lion Oil and Fats) 47 mg / m ² compound (21) (hardener) Amount at which the swelling ratio in water is 80% Compound (22) 1.2 × 10 ⁻³ mol / mol Ag Above The emulsion protection lower layer and the upper layer were coated on the emulsion layer.

(Emulsion Protecting Lower Layer) The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin would be 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.8g / m ² compound (15) 1mg / m ² 1,5-dihydroxy-2-benzaldoxime 14mg / m ² C ₂ H ₅ SO ₂ SNa 3mg / m ² compound (19) 3 mg / m ² sodium p-dodecylbenzenesulfonate 7 mg / m ²

(Preparation of Emulsion Protecting Upper Layer Coating Solution and Its Coating)
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.45 g / m ² amorphous silica matting agent (average particle size 4.4 μm) 40 mg / m ² amorphous silica matting agent (average particle size 3.6 μm) 10 mg / m ² compound (15) 1mg / m ² compound (19) 8mg / m ² solid disperse dye - (24) 68mg / m ² Liquid paraffin 21 mg / m ² N-perfluorooctane sulfonyl -N- propyl glycine Potajiumu 5 mg / m ² p- Sodium dodecylbenzenesulfonate 29 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

(Conductive layer) The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 186 mg / m ² gelatin (Ca ⁺⁺ content 2700 ppm) 0.06 g / m ² sodium p-dodecylbenzenesulfonate 13 mg / m ² dihexyl- α-Sulfosuccinate sodium 12 mg / m ² compound (19) 12 mg / m ² compound (15) 1 mg / m ²

(Back layer) The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin would be 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94g / m ² of polymethyl methacrylate particles (average particle size 4.7μ) 7mg / m ² Compound (11) 233mg / m ² Compound (13) 21mg / m ² Compound (23 ) 146 mg / m ² compound (15) 3 mg / m ² sodium p-dodecylbenzenesulfonate 68 mg / m ² dihexyl-α-sulfosuccinate sodium 21 mg / m ² C ₈ F ₁₇ SO ₃ Li 4 mg / m ² N-per the amount of perfluorooctane sulfonyl -N- propyl glycine Potajiumu 6 mg / m ² sodium sulfate 177 mg / m ² compound (21) (hardener) swelling rate in water is 90%

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate supports (thickness: 100 μm) were coated with first and second undercoat layers having the following compositions on both sides. (Undercoat first layer) Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Colloidal silica (Snowtex) ZL; particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added, and the coating solution adjusted to pH = 6 was dried at a drying temperature of 180 ° C. for 2 minutes. Film thickness is 0.9
It was applied so that it became μ.

(Second Layer of Undercoat Layer) Gelatin 1 g Methylcellulose 0.05 g Compound (25) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound (15) 3.5 × 10 ^-3 g Acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm, to prepare a support with an undercoat layer. In addition, the coating method, drying conditions, etc. were performed as follows. <Coating method> On the support provided with the undercoat layer, an emulsion layer, an emulsion protective lower layer,
In the order of the emulsion protection upper layer, simultaneous multi-layer coating is performed while adding a hardener solution by a slide hopper method while maintaining at 35 ° C.
After passing through the cool air setting zone (5 ° C.), the conductive layer and the back layer are arranged in the order from the side closer to the support on the side opposite to the emulsion surface,
Similarly, simultaneous multi-layer coating was performed by adding a hardener solution by a slide hopper method, and a cold air setting zone (5 ° C.) was applied. At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time is 120 m / min
Met.

<Drying conditions> After setting, the product was dried with a dry air of 30 ° C. until the weight ratio of water / gelatin reached 800%, and then 8
Dry 200 to 200% with dry air at 35 ° C and 30%, apply air as it is, and after 30 seconds from when the surface temperature reaches 34 ° C (assuming the end of drying), dry for 1 minute at 48 ° C and 2% air. did. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800% and 35 from 800 to 200%.
Seconds, 5% from 200% to the end of drying.

This sensitive material was wound up at 40 ° C. at 23 ° C., then cut under the same environment, and placed in a barrier bag which was conditioned for 6 hours to obtain 4 pieces.
After humidifying at 0 ° C. 10% for 8 hours, the sample was sealed with cardboard conditioned at 23 ° C. 40% for 2 hours to prepare a sample. When the humidity inside the barrier bag was measured, it was 40%.

<Preparation of Photosensitive Material (4)> Preparation of Emulsion D 1-liquid water 1-liter gelatin 20 g sodium chloride 2.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2-liquid water 400 ml Silver nitrate 100g 3 liquid water 400ml Sodium chloride 21.9g Potassium bromide 31.5g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 10ml Potassium hexachlorodium (III) (0.001% aqueous solution) 5ml

Solution 2 and solution 3 were added simultaneously to solution 1 maintained at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. Fourth liquid 400ml Silver nitrate 100g Five liquid 400ml Sodium chloride 25.4g Potassium bromide 24.5g

Thereafter, it was washed with water by a flocculation method according to a conventional method, and 62 g of gelatin was added. pH
5.9, pAg was adjusted to 7.5, sodium thiosulfate 2.0 mg, chloroauric acid 8.0 mg, triphenylphosphine selenide 2.0 mg, sodium benzenethiosulfonate 4
mg and 1 mg of sodium benzenesulfinate were added and chemically sensitized at 60 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
150 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 60 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion A having an average grain size of 0.24 μm was obtained. Preparation of coated sample Emulsion D was added with 7.0 × 10 ^-4 mol / mol Ag of sensitizing dye and subjected to spectral sensitization. Furthermore, Kbr 4.0 × 10 ^-3
Mol / mol Ag, compound 2.5 × 10 ⁻⁴ mol / mol A
g, compound 8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.5 × 10 ⁻² mol / mol Ag, compound 26 2.
0 × 10 ^-4 mol / mol Ag, compound 5.0 × 10 ^-4
Mol / mol Ag, 40 wt% polyethyl acrylate latex to gelatin, 25 wt% to gelatin, colloidal silica with a particle size of 10 mμ, and 4 wt% compound to gelatin were added to the polyester support. Ag 3.2 g / m ² , gelatin 1.8 g / m ²
Was applied. An upper protective layer and a lower protective layer having the following composition were applied thereon. Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent with an average of 3.5 μm 35 mg / m ² compound (gelatin dispersion) 20 mg / m ² Colloidal silica with a particle size of 10 to 20 μm 30 mg / m ² compound 5 mg / m ² dodecyl Sodium benzenesulfonate 20 mg / m ² compound 20 mg / m ² protective layer lower layer gelatin 0.5 g / m ² compound 10 mg / m ² compound 23 50 mg / m ² compound 27 20 mg / m ² 1,5-dihydroxy-2-benzald Xime 10 mg / m ² Polyethyl acrylate latex 250 mg / m ²

The support of the light-sensitive material (4) has a back layer and a back protective layer having the following composition. Back layer Gelatin 2.5 g / m ² Sodium dodecylbenzenesulfonate 30 mg / m ² Compound (11) 50 mg / m ² Compound (12) 30 mg / m ² Compound (13) 30 mg / m ² Compound (28) 90 mg / m ² Compound 140 mg / m ² back protective layer Gelatin 1.0 g / m ² 1,3-divinylsulfonyl-2-propanol 20 mg / m ² Polymethylmethacrylate fine particles (average particle size 3.5 μm) 10 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ²

The structures of the compounds used in the light-sensitive materials (1) to (4) are shown below.

[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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The composition of the developer (1) per liter of concentrated solution is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.24 g 4-Hydroxymethyl-4-methyl-1-phenyl-3 -Pyrazolidone 1.35 g Compounds of general formulas (1) to (3) listed in Table 1 (addition amount is 3 times per concentrate) Sodium erythorbate 9.0 g Diethylene glycol 60.0 g pH 10.7 When using 1 part of the above concentrate Dilute with 2 parts of water. The pH of the working solution is 10.5.

The composition of the solid developer (developer (2)) is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (bulk powder) 1463.0 g Sodium sulfite (bulk powder) 1446.0 g Potassium carbonate 1462.0 g Hydroquinone (briquette) 1440.0 g Collect into briquettes below. Diethylenetriamine / pentaacetic acid 142.0 g 5-Methylbenzotriazole 140.35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 141.5 g Compounds of general formulas (1) to (3) described in Table 1 3- (5 -Mercaptotetrazol-1-yl) Sodium benzenesulfonate 140.1 g Sodium erythorbate 146.0 g Potassium bromide 146.6 g Dissolve this in water to make 1 liter. pH 10.5

Here, in the form of raw materials, the raw powder was used as it is a general industrial product, and the alkali metal salt beads were commercially available. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treating agent was filled in a high-density polyethylene foldable container, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, a dissolution and replenishment device having an automatic opening mechanism disclosed in Japanese Patent Application Nos. 7-235499 and 7-235498 was used.

The formulation of the fixing solution (1) per liter of concentrated solution is shown below. Ammonium thiosulfate 360 g Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.09 g Sodium thiosulfate ・ pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8.7 g Sodium gluconate 5.1 g Aluminum sulfate 25.2 g pH 4.85 Before use, dilute 2 parts of water to 1 part of the above concentrated solution. The pH of the working solution is 4.8.

The composition of the solid fixing agent (fixing solution (2)) is shown below. A agent (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (bulk powder) 19.0 g Sodium metabisulfite (bulk powder) 18.0 g Anhydrous sodium acetate (bulk powder) 42.0 g B agent (liquid) Ethylenediamine / tetraacetic acid・ 2Na ・ dihydrate 0.03 g anhydrous citric acid 3.7 g sodium gluconate 1.7 g aluminum sulfate 8.4 g sulfuric acid 2.1 g Dissolve in water to make 50 ml. Agent A and Agent B were dissolved in water to make 1 liter. pH 4.8

Ammonium thiosulfate (compact) was prepared by spray-drying flakes prepared by pressing under pressure with a roller compactor and crushing them into chips of irregular shape of about 4 to 6 mm, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. Japanese Patent Application No. 7-23549 for dissolution and replenishment
9. The dissolution replenishing device having an automatic opening mechanism disclosed in Japanese Patent Application No. 7-235498 was used.

Example 1 An automatic developing machine FG-680AG manufactured by Fuji Photo Film Co., Ltd. was filled with a developing solution and a fixing solution, and the light-sensitive materials (1) to (4) and the output light-sensitive material LS-5500 manufactured by the same company, and dupe paper DU- Sensitometry of 150 WP was performed. The photosensitive materials (1), (2), and (4) were processed at a developing temperature of 35 ° C., a fixing temperature of 34 ° C., and a developing time of 30 seconds. The photosensitive material (3) was processed by setting the developing temperature to 38 ° C., the fixing temperature to 37 ° C. and the developing time to 20 seconds. The exposure conditions of each photosensitive material were as follows. Light-sensitive material (1) Exposure through a step wedge through a 633nm interference filter with xenon flash light with an emission time of 10 ^-6 seconds Light-sensitive material (2) Light emission time through a step wedge through an interference filter with a peak at 488nm 10 ^-5 Second exposure with xenon flash light Sensitive material (3) Exposure through step wedge with Dainippon Screen P-627FM printer Sensitive material (4) Exposure with 3200 ° K tungsten light through step wedge LS-5500 Peak at 488 nm Exposure through a step wedge through an interference filter with a xenon flash light with a light emission time of 10 ^-4 seconds DU-150WP Exposure through a step wedge with a Dainippon Screen P-627FM printer Table 1 Minimum density (Dmin) or Sensitivity at concentration 3.0 (S3.
The difference between 0) and the blank was shown. Dmin difference + 0.03 or less, S3.
0 The allowable range is within ± 0.02.

Example 2 After processing 100 m ² of the unexposed light-sensitive material (3) under the automatic developing machine and processing conditions of Example 1, the developing solution was filtered through a 0.45 m microfilter to determine the silver content of the filtrate. It was measured. The developing solution was only replenished in a reduced amount. The results are shown in Table 1 (column of silver elution amount)
It was shown to. The embodiments of the present invention show excellent ability to suppress silver elution,
It can be seen that the effect of suppressing silver elution is superadditively compared to the case where each compound is used alone.

Example 3 In Example 2, the developer replenishment rate was 160 ml / m ² , and the fixing solution replenishment rate was 160 ml / m ² .
The photosensitive material (3) was imagewise exposed with a blackening rate of 20% at 255 ml / m ² and the same treatment as in Example 2 was carried out for 10 days, and then unexposed contact paper KU-150WP (4) (Cut into pieces) was processed to observe the degree of dirt attachment. The results are shown in Table 1 (dirt column). A level of 4 or higher is a level at which there is no practical problem.
Further, after this treatment, the same treatment as in Example 1 was performed, and the same result as in Example 1 was obtained. In addition, the generation state of sludge and the like in the developing tank was observed. The results are shown in Table 1 (precipitation occurrence column).

[0179]

[Table 1]

Example 4 Even when the same experiment as in Examples 1 to 3 was carried out using the solid developer (developing solution (2)) and the solid fixing agent (fixing solution (2)), the same results were obtained. Obtained.

Example 5 In Example 3, the same result was obtained even when the developing machine was FG-680AS manufactured by the same company and the developing time was set to 11 seconds and the same processing was performed.

[0182]

The combined use of the compounds of the present invention resulted in superadditivity in the silver elution suppressing ability, and as a result, it was possible to obtain a very good silver stain preventing effect without affecting the photographic properties. .

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[Procedure amendment]

[Submission date] October 30, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0146

[Correction method] Change

[Correction contents]

Thereafter, the flocculation is performed according to a conventional method.
The mixture was washed with water by the spin method and 40 g of gelatin was added. pH
5.7, pAg adjusted to 7.5, sodium thiosulfate
1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine
Selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate at 55 ° C
Chemically sensitized to obtain optimum sensitivity. As a stabilizer
4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene 100mg, phenoxy as preservative
Ethanol is added and finally contains 70 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion B having an average grain size of 0.23 μm was obtained.
Was. Preparation of coating sample Emulsion B: Sensitizing dye 2.0 × 10^-FourMol / mol Ag, increase
Sensitizing dye 7.0 × 10 ^-FourAdd mol / mol Ag to increase spectral
I gave a feeling. Furthermore, Kbr 3.4 × 10^-FourMol / mol A
g, compound 5.0 × 10^-FourMol / mol Ag, compound
8.0 x 10^-FourMol / mol Ag, hydroquinone 1.2
× 10^-2Mol / mol Ag, compound 1.8 × 10^-FourMo
Le / mol Ag, compound 3.5 × 10^-FourMol / mol A
g, and 30 wt% of polyethyl acetate based on gelatin.
15 wt% of acrylate latex and gelatin
4 for colloidal silica and gelatin with a particle size of 10 mμ
Add wt% compound to polyester support
Ag 3.4 g / m^Two, Gelatin 1.5g / m^TwoTo be
Applied. On top of this, a protective layer and a protective layer having the following composition
A lower layer was coated with a UL layer having the following composition below. Upper layer of protective layer Gelatin 0.3 g / m^Two An average of 3.5 μm silica matting agent 25 mg / m^Two Compound (gelatin dispersion) 20 mg / m^Two Colloidal silica having a particle size of 10 to 20 μm 30 mg / m^Two Compound 5mg / m^Two Sodium dodecylbenzene sulfonate 20mg / m^Two Compound 20mg / m^Two Lower layer of protective layer Gelatin 0.5g / m^Two Compound 15mg / m^Two 1,5-dihydroxy-2-benzaldoxime 10 mg / m^Two Polyethyl acrylate latex 250mg / m^Two UL layer gelatin 0.5g / m^Two Polyethyl acrylate latex 150mg / m^Two Compound 40mg / m^Two

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0148

[Correction method] Change

[Correction contents]

<Preparation of Coating Sample> (Silver Halide Emulsion Layer) The following compound was added to Emulsion C to give a gelatin coating amount of 0.9 g on a support described below including an undercoat layer.
/ M ^2, the coating amount of silver coated with silver halide emulsion layer as a 2.75 g / m ^2. N-oleyl-N-methyltaurine sodium salt 19 mg / m ² compound (16) 20 mg / m ² 3- (5-mercaptotetrazole) -benzenesulfonic acid sodium 11 mg / m ² compound (17) 13 mg / m ² ascorbic acid 1 mg / M ² compound (18) 15 mg / m ² compound (19) 70 mg / m ² acetic acid Amount that makes the film surface pH 5.2 to 6.0 Compound (20) 950 mg / m ² Riborane-1400 (Made by Lion Oil and Fats) 47 mg / m ² Compound (21) (hardener) Amount at which the swelling ratio in water is 80% Compound (22) 1.2 × 10 ⁻³ mol / mol Ag An emulsion protection lower layer and an emulsion protection lower layer above the above emulsion layer. The top layer was applied.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0160

[Correction method] Change

[Correction contents]

Thereafter, it was washed with water by a flocculation method according to a conventional method, and 62 g of gelatin was added. pH
5.9, pAg was adjusted to 7.5, sodium thiosulfate 2.0 mg, chloroauric acid 8.0 mg, triphenylphosphine selenide 2.0 mg, sodium benzenethiosulfonate 4
mg and 1 mg of sodium benzenesulfinate were added and chemically sensitized at 60 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
150 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 60 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion D having an average grain diameter of 0.24 μm was obtained. Preparation of coated sample Emulsion D was added with 7.0 × 10 ^-4 mol / mol Ag of sensitizing dye and subjected to spectral sensitization. Furthermore, Kbr 4.0 × 10 ^-3
Mol / mol Ag, compound 2.5 × 10 ⁻⁴ mol / mol A
g, compound 8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.5 × 10 ⁻² mol / mol Ag, compound 26 2.
0 × 10 ^-4 mol / mol Ag, compound 5.0 × 10 ^-4
Mol / mol Ag, 40 wt% polyethyl acrylate latex to gelatin, 25 wt% to gelatin, colloidal silica with a particle size of 10 mμ, and 4 wt% compound to gelatin were added to the polyester support. Ag 3.2 g / m ² , gelatin 1.8 g / m ²
Was applied. An upper protective layer and a lower protective layer having the following composition were applied thereon. Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent with an average of 3.5 μm 35 mg / m ² compound (gelatin dispersion) 20 mg / m ² Colloidal silica with a particle size of 10 to 20 μm 30 mg / m ² compound 5 mg / m ² dodecyl Sodium benzenesulfonate 20 mg / m ² compound 20 mg / m ² protective layer lower layer gelatin 0.5 g / m ² compound 10 mg / m ² compound 23 50 mg / m ² compound 27 20 mg / m ² 1,5-dihydroxy-2-benzald Xime 10 mg / m ² Polyethyl acrylate latex 250 mg / m ²

Claims (2)

[Claims] 1. A method of developing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer, wherein at least one of the compounds represented by formula (1) is used.
A method for processing a silver halide photographic light-sensitive material, which comprises using a developing solution containing a seed and at least one compound represented by the general formula (2) or (3). Embedded image In the general formula (1), R _{1 to} R ₃ represent a hydrogen atom, a halogen atom or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, and at least one is a mercapto group. Further, two kinds of radicals obtained by removing one arbitrary hydrogen atom of carbon forming the triazine ring may be bonded to each other to form a bis type structure. Embedded image In the general formula (2), R ₄ and R ₅ may be the same or different and represent the same groups as R _{1 to} R _{3 in} the general formula (1). However, it does not necessarily have to be a mercapto group.
M is a hydrogen atom or a cation. Embedded image In the general formula (3), Z is a nonmetallic atomic group or at least one O atom necessary for forming a 5-membered heterocycle having a total nitrogen number of 1 or 3 in combination with C and N, and / or Alternatively, it represents a non-metal atomic group necessary for forming a 5-membered heterocycle in cooperation with S atom and C and N. Further, it may be condensed with a hydrocarbon ring or a hetero ring. M is a hydrogen atom or a cation. 2. The replenishment rate of the developing solution according to claim 1 is 330 ml / m ^2.
A method of processing a silver halide photographic light-sensitive material, characterized in that: