JPH0961955A - Black-and-white silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photosensitive material capable of rapid processing and low replenishment processing and forming an image high in sensitivity and low in fog and small in black spots by chemically sensitizing a silver halide emulsion specified in a silver chloride content with a specified compound. SOLUTION: The silver halide emulsion layer formed on the support of the photosensitive material has a silver chloride content of 60-100mol% and it is chemically sensitized with at least one kind of compound selected mainly from formulae I-III in which each of R11 -R13 is an aliphatic or aromatic or heterocyclic group and R11 and R12 may combine with each other to form a carbon ring or hetero ring; X11 is a selenium or tellurium atom; and each of R21 , R22 , R23 , R31 , and R32 is an alkyl or aryl or heterocyclic group. These compounds of formulae I-III and the like can be added as a solution of water or a water- miscible organic solvent, such as methanol or ethanol, or dispersed fine crystals at an optional time in the manufacture of the emulsion but it is preferred to add it at the time of starting the chemical sensitization usually in an amount of 3×10<-8> -1×10<-3> mol/mol of silver halide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black and white silver halide photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material), and more specifically, a silver halide photographic light-sensitive material for printing plate making (hereinafter
(Also referred to simply as a photosensitive material for printing plate making) and a processing method thereof.

[0002]

2. Description of the Related Art A silver halide emulsion containing 60 mol% or more of silver chloride has been conventionally used in a light-sensitive material for printing plate making in order to reproduce an image in high contrast.

Further, in the light-sensitive material for printing plate making, a photographic technique capable of reproducing a super-high contrast image is used in view of photographic characteristics, and various photographic techniques are known. Among them, for example, a black and white silver halide photographic light-sensitive material containing a hydrazine derivative as shown in U.S. Pat. No. 4,269,929 and a black and white containing a nucleation accelerator as disclosed in JP-A-4-98239. A silver halide photographic light-sensitive material is known. Similarly, a black and white silver halide photographic light-sensitive material containing a tetrazolium compound as disclosed in JP-A-59-79244 is also known.

Conventionally, a black-and-white silver halide photographic light-sensitive material in which these silver halide emulsions containing 60 mol% or more of silver chloride are used, and a technique for achieving the above-mentioned ultra-high contrast image reproduction are known. When the black-and-white silver halide photographic light-sensitive material used is chemically sensitized with conventionally known sodium thiosulfate or the like, if sensitivity is increased, fog is increased or there is a problem with storage stability over time. There is a problem that a sand-like minute spot, which is a so-called black spot, is likely to occur in the exposed portion.

On the other hand, a black-and-white silver halide photographic light-sensitive material, especially a light-sensitive material for printing plate making, is generally developed, fixed, and exposed after exposure.
Photographic processing is carried out in an automatic processor having four processes of washing and drying.

Recently, it has been required to shorten the development processing time for black and white silver halide photographic light-sensitive materials. Conventionally, the total processing time (Dry to Dry) from the time when the leading edge of the film is inserted into the automatic developing machine having the developing tank, the fixing tank and the washing tank or the stabilizing tank until it comes out of the drying zone is usually 90 seconds or more. However, in recent years, it has become necessary to perform rapid processing with a total processing time (Dry to Dry) of 60 seconds or less.

Further, in recent years, due to the growing concern about environmental problems, reduction of waste liquid for photographic processing has been demanded. There are several methods for reducing the photographic processing waste liquid, and among them, the reduction of the development replenisher and the fixing replenisher is most effective.

Conventionally, the developing replenishing amount and the fixing replenishing amount were usually 400 ml or more per 1 m ² of the area of the photosensitive material to be processed, but in recent years, the developing replenishing amount and the fixing replenishing amount are processed. It has become necessary to process less than 300 ml per 1 m ^{2 of} material area. In the case of carrying out these rapid processing and low replenishment processing, the above-mentioned problems became more serious. Further, there is a problem that the processing liquid is fatigued and the photographic performance is changed.

Further, in order to reduce environmental pollution, it is effective to use a developing solution containing no hydroquinone, but in this case, the above-mentioned problems are further serious.

[0010]

With respect to the above problems, an object of the present invention is to enable rapid processing and low replenishment processing,
It is an object of the present invention to provide a black-and-white silver halide photographic light-sensitive material having high sensitivity and less fog, and a processing method thereof. Another object of the present invention is to provide a black-and-white silver halide photographic light-sensitive material having less black spots and a processing method thereof. Still another object of the present invention is to provide a black-and-white silver halide photographic light-sensitive material and a method of processing the same, in which the processing solution is fatigued and its performance is less deteriorated even after storage for a long time.

[0011]

The above object of the present invention is achieved by the following constitution.

1. A silver halide emulsion layer is provided on a support, and the silver halide emulsion contains 60 mol% or more and 100 mol% or more.
A black-and-white silver halide photographic light-sensitive material containing the following silver chloride, wherein the silver halide emulsion is chemically sensitized with at least one compound selected from the following general formulas [1] to [6].

[0013]

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In the general formula [1], R ₁₁ , R ₁₂ and R ₁₃ each represent an aliphatic group, an aryl group or a heterocyclic group, and R ₁₁ and R
₁₂ may combine with each other to form a carbocycle or a heterocycle. X ₁₁ represents a selenium atom or a tellurium atom.

In the general formula [2], R ₂₁ , R ₂₂ and R ₂₃ are
Each represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula [3], R ₃₁ and R ₃₂ are respectively
It represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula [4], R ₄₁ and R ₄₂ are respectively
An alkyl group, an aryl group, or a group which forms a heterocycle with X ₄₁ by being bonded between R ₄₁ and R _42, and Ar represents an aryl group. X ₄₁ represents a selenium atom or a tellurium atom, W represents a sulfonyl group or a carbonyl group, and n
Represents an integer of 0 or 1.

In the general formula [5], R ₅₁ , R ₅₂ , R ₅₃ and R
₅₄ represents an alkyl group or an aryl group, and X ₅₁ represents an oxygen atom or a sulfur atom.

In the general formula [6], R ₆₁ and R ₆₂ are respectively
It represents an alkyl group, an aryl group, or a group which is bonded between R ₆₁ and R ₆₂ to form a condensed carbocycle or a condensed heterocycle.

2. Having a silver halide emulsion layer on a support,
At least one layer selected from the silver halide emulsion layer and / or its adjacent layer contains a hydrazine derivative, and the silver halide emulsion is chemically enhanced with at least one compound selected from the above formulas [1] to [6]. A black-and-white silver halide photographic light-sensitive material characterized by being perceived.

3. A silver halide emulsion layer is provided on a support, and a pyridinium compound is contained in at least one layer selected from the silver halide emulsion layer and / or its adjacent layer, and the silver halide emulsion has the above general formula [1] to A black-and-white silver halide photographic light-sensitive material, which is chemically sensitized with at least one compound selected from [6].

4. A silver halide emulsion layer is provided on a support, a tetrazolium compound is contained in at least one layer selected from the silver halide emulsion layer and / or its adjacent layer, and the silver halide emulsion has the above general formula [1] to A black-and-white silver halide photographic light-sensitive material, which is chemically sensitized with at least one compound selected from [6].

5. When processed with an automatic developing machine for black and white silver halide photographic light-sensitive materials having a developing tank, a fixing tank and a washing tank or a stabilizing tank, the developing replenishing amount and the fixing replenishing amount are respectively 3
5. The method for processing a black-and-white silver halide photographic light-sensitive material as described in 1, 2, 3 or 4 above, wherein the processing is carried out while replenishing in an amount of 0 ml or more and 300 ml / m ² or less.

6. When the black-and-white silver halide photographic light-sensitive material described in 1, 2, 3 or 4 above is processed by an automatic processor for black-and-white silver halide photographic light-sensitive material having a developing tank, a fixing tank and a washing tank or a stabilizing tank, A black-and-white silver halide photographic light-sensitive material having a total processing time (Dry to Dry) of 10 seconds to 60 seconds from the time when the leading edge of the film of the light-sensitive material is inserted into the automatic processor to the time when it comes out of the drying zone. Material processing method.

[7] 7. The method for processing a black-and-white silver halide photographic light-sensitive material as described in 5 or 6, wherein the black-and-white silver halide photographic light-sensitive material as described in 1, 2, 3 or 4 is processed with a developer containing no hydroquinone. .

The present invention will be described in more detail.

The black and white silver halide photographic light-sensitive material of the present invention is chemically sensitized with at least one compound selected from the above formulas [1] to [6].

The general formulas [1] to [6] will be described.

In the general formula [1], R ₁₁ , R ₁₂ and R
_The aliphatic group represented by ₁₃ is a linear or branched alkyl group (for example, methyl, ethyl, iso-propyl, t-
Butyl, iso-butyl, t-pentyl, hexyl, and other groups), cyclic alkyl groups (eg, cyclopropyl,
Cyclopentyl, cyclohexyl, etc.) and unsaturated alkyl groups (eg, vinyl, 1-propenyl, 1-
Each group such as butenyl and 1-propynyl).

The aryl group represented by R ₁₁ , R ₁₂ and R ₁₃ includes a phenyl group and a naphthyl group, and the heterocyclic group includes groups such as furyl, thienyl and pyridyl. Examples of the carbocyclic group formed by combining R ₁₁ and R ₁₂ with each other include groups such as cyclopentane, cyclohexane and adamantane, and examples of the heterocyclic group include groups such as pyrrolidine and piperidine. Can be mentioned.

The above-mentioned aliphatic groups represented by R ₁₁ , R ₁₂ and R ₁₃ may have a substituent at any position, and specific examples of the substituent include, for example, a halogen atom (chlorine atom, Bromine atom, fluorine atom, iodine atom), trifluoromethyl group, alkoxy group (eg, unsubstituted alkoxy groups such as methoxy, ethoxy, butoxy, etc., substituted alkoxy groups such as 2-methoxyethoxy, benzyloxy, etc.), hydroxy group , A cyano group, an aryloxy group (eg, substituted or unsubstituted groups such as phenoxy, tolyloxy, etc.), or an aryl group (eg, substituted or unsubstituted groups such as phenyl, m-tolyl, p-chlorophenyl, carboxyphenyl, etc.) Group), a styryl group, a heterocyclic group (for example, each group such as furyl and thienyl), a carbamoyl group (for example, carbamoyl, N-ethylcarba). Each group such as moyl), a sulfamoyl group (for example, each group such as sulfamoyl, N, N-dimethylsulfamoyl), an acylamino group (for example, each group such as acetylamino, propionylamino, benzoylamino), an acyl group ( For example, each group such as acetyl and benzoyl), an alkoxycarbonyl group (for example, a group such as ethoxycarbonyl), a sulfonamide group (for example, each group such as methanesulfonylamide, benzenesulfonamide), a sulfonyl group (for example, methanesulfonyl, p-
Each group such as toluenesulfonyl) and any group such as carboxy group and sulfo group.

The aryl group and heterocyclic group represented by R ₁₁ , R ₁₂ and R ₁₃ , and the carbocyclic group and heterocyclic group formed by R ₁₁ and R ₁₂ being bonded to each other are substituted at arbitrary positions. may have a group, other aliphatic group described for R _11, R ₁₂ and R _13, include the substituents described as examples of the substituents of R _11, R ₁₂ and R _13.

Specific examples of the selenium and tellurium compounds represented by the general formula [1] are shown below, but the compounds of the present invention are not limited to these.

[0034]

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[0035]

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In the general formulas [2] and [3], R ₂₁ ,
Examples of the alkyl group represented by R ₂₂ , R ₂₃ , R ₃₁ and R ₃₂ include linear or branched alkyl groups (for example, methyl, ethyl, iso-propyl, t-butyl, iso-butyl,
t-pentyl, each group such as hexyl), a cyclic alkyl group (for example, each group such as cyclopropyl, cyclopentyl, cyclohexyl) and an unsaturated alkyl group (for example, vinyl, 1-propenyl, 1-butenyl, 1-). Each group such as propynyl).

The aryl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ and R ₃₂ includes a phenyl group and a naphthyl group, and the heterocyclic group includes groups such as furyl, thienyl and pyridyl. Can be mentioned.

The aforementioned alkyl groups represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ and R ₃₂ may be substituted at any position,
Specific examples include, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), trifluoromethyl group, alkoxy group (eg, unsubstituted alkoxy groups such as methoxy, ethoxy, butoxy, and 2-methoxyethoxy). , Substituted alkoxy groups such as benzyloxy), hydroxy groups, cyano groups, aryloxy groups (eg substituted or unsubstituted groups such as phenoxy and tolyloxy), or aryl groups (eg phenyl, m-tolyl, p). -Substituted or unsubstituted groups such as chlorophenyl and carboxyphenyl), styryl groups, heterocyclic groups (eg, groups such as furyl and thienyl), carbamoyl groups (eg, groups such as carbamoyl and N-ethylcarbamoyl) , A sulfamoyl group (for example, each group such as sulfamoyl, N, N-dimethylsulfamoyl, etc.) Acylamino group (eg, groups such as acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, groups such as acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, group such as ethoxycarbonyl), sulfonamide group (eg, , Methanesulfonylamide, benzenesulfonamide and the like), sulfonyl group (eg, methanesulfonyl, p-
Each group such as toluenesulfonyl) and any group such as carboxy group and sulfo group.

The aryl group and heterocyclic group represented by _{R 21, R 22, R 23} , R 31 and R ₃₂ each may have a substituent at any position, R _21, R _22, R _23, other alkyl group described for R ₃₁ and R _32, substituents described as examples of the substituents of R _21, R _22, R _23, R ₃₁ and R ₃₂ can be mentioned.

Specific examples of the selenium compounds represented by the general formulas [2] and [3] are shown below, but the compounds of the present invention are not limited thereto.

[0041]

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[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

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The compounds represented by the general formulas [1] to [3] of the present invention are described, for example, in Berichte Vol. 105, page 454 (197).
0), Vol. 106, p. 1012 (1973), etc., and can be easily synthesized by a conventionally known method.

The compound represented by the general formula [4] will be described.

In the above general formula [4], R ₄₁ and R ₄₂
The alkyl group represented by is a linear or branched group (for example, methyl, ethyl, iso-propyl, t-butyl,
each group such as iso-butyl, t-pentyl, hexyl),
And a cyclic group (for example, each group such as cyclopropyl, cyclopentyl, cyclohexyl, etc.). R ₄₁ and R
_The heterocycle formed by ₄₂ bonded to each other together with a selenium atom includes a monocyclic ring and a condensed ring, and examples thereof include a heterocycle such as selenolane, selenane, 1,4-oxaselenane, and dibenzo [b, d] selenophene. A ring is included.

Examples of the aryl group represented by R ₄₁ , R ₄₂ and Ar include a phenyl group and a naphthyl group. R ₄₁
And the alkyl group represented by R ₄₂ may have a substituent at any position, and specific examples of the substituent include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom,
(Iodine atom), trifluoromethyl group, alkoxy group (eg, unsubstituted alkoxy groups such as methoxy, ethoxy and butoxy, substituted alkoxy groups such as 2-methoxyethoxy and benzyloxy), hydroxyl group, cyano group, aryloxy group A group (eg, substituted or unsubstituted group such as phenoxy or tolyloxy) or an aryl group (eg,
Substituted or unsubstituted groups such as phenyl, m-tolyl, p-chlorophenyl, and carboxyphenyl), styryl groups, heterocyclic groups (eg, groups such as furyl and thienyl), carbamoyl groups (eg, carbamoyl, N-). Each group such as ethylcarbamoyl), a sulfamoyl group (for example, each group such as sulfamoyl, N, N-dimethylsulfamoyl),
Acylamino group (eg, groups such as acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, groups such as acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, group such as ethoxycarbonyl), sulfonamide group (eg, , Methanesulfonamide, benzenesulfonamide, etc.), sulfonyl groups (eg,
Each group such as methanesulfonyl and p-toluenesulfonyl)
Examples include arbitrary groups such as a carboxyl group and a sulfo group.

An aryl group represented by R ₄₁ , R ₄₂ and Ar,
And may have a substituent at any position on the heterocyclic ring formed by R ₄₁ and R ₄₂ and selenium atoms, other alkyl group described for R ₄₁ and R _42, R ₄₁ and R ₄₂ The substituents described as specific examples of the substituents of are mentioned.

Specific examples of the selenium and tellurium compounds represented by the general formula [4] are shown below, but the compounds of the present invention are not limited thereto.

[0051]

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[0052]

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The compound represented by the general formula [4] of the present invention is described in, for example, Journal of the American Chemical Society, 77, 4929 (1955).
, Tetrahydrone, 36, 3865 (1974)
, Tetrahydrone Letters, p. 649 (1975)
), Pp. 901 (1982), Journal of
The Organic Chemistry USSR, Volume 14,
807 (1978), 13: 202 (197)
7), 15: 804 (1979), 16
Volume, 2210 (1980), 17, 341 (1981) Justus Liebigs Annalen del Chemie 715, 68 (1962), 7
It can be easily synthesized by a conventionally known method described in Volume 12, Page 1 (1968) and the like.

The general formula [5] will be described.

In the above general formula [5], R ₅₁ , R ₅₂ ,
The alkyl group represented by R ₅₃ and R ₅₄ is a linear or branched group (for example, methyl, ethyl, iso-propyl,
t-butyl, iso-butyl, t-pentyl, hexyl, etc.) and a cyclic group (eg, cyclopropyl, cyclopentyl, cyclohexyl, etc.).

Examples of the aryl group represented by R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ include a phenyl group and a naphthyl group. The aforementioned alkyl group represented by R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ may have a substituent at any position, and specific examples of the substituent include, for example, a halogen atom (chlorine atom, bromine). Atom, fluorine atom, iodine atom), trifluoromethyl group, alkoxy group (eg, unsubstituted alkoxy groups such as methoxy, ethoxy and butoxy, substituted alkoxy groups such as 2-methoxyethoxy and benzyloxy), hydroxy group, Cyano group, aryloxy group (eg, substituted or unsubstituted group such as phenoxy or tolyloxy), or aryl group (eg, substituted or unsubstituted group such as phenyl, m-tolyl, p-chlorophenyl or carboxyphenyl) ), A styryl group, a heterocyclic group (for example, each group such as furyl and thienyl), a carbamoyl group (for example, carbamoyl, N-ethylcarbamo). Each group), a sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, etc.), an acylamino group (eg, acetylamino, propionylamino, benzoylamino, etc.), an acyl group ( For example, each group such as acetyl and benzoyl), an alkoxycarbonyl group (for example, a group such as ethoxycarbonyl), a sulfonamide group (for example, a group such as methanesulfonamide, benzenesulfonamide),
A sulfonyl group (for example, each group such as methanesulfonyl, p-toluenesulfonyl, etc.), and a carboxyl group, a sulfo group, or any other group. X ₅₁ represents an oxygen atom or a sulfur atom.

[0057] Aryl groups represented by R _51, R _52, R ₅₃ and R ₅₄ may have a substituent at any position, R _51,
In addition to the alkyl group described for R ₅₂ , R ₅₃ and R ₅₄ , R ₅₁ ,
The substituents described as specific examples of the substituents of R ₅₂ , R ₅₃ and R ₅₄ can be mentioned.

Specific examples of the selenium compound represented by the general formula [5] are shown below, but the compound of the present invention is not limited thereto.

[0059]

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[0060]

[Chemical 12]

[0061]

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The compound represented by the general formula [5] of the present invention is described in, for example, Journal of the Chemical Society C, page 3187 (1971), Journal.
It can be easily synthesized by a conventionally known method described in, for example, The of the Chemical Society Chemical Communication, page 177 (1973).

In the general formula [6], the alkyl group represented by R ₆₁ and R ₆₂ is a linear or branched group (for example, methyl, ethyl, iso-propyl, t-butyl, is).
each group such as o-butyl, t-pentyl, and hexyl), and a cyclic group (for example, cyclopropyl, cyclopentyl,
Each group such as cyclohexyl). The condensed carbocycle formed by R ₆₁ and R ₆₂ bonded to each other is saturated,
It includes an unsaturated ring, and examples thereof include a cyclopentane ring, a cyclohexane ring, and a benzene ring. Further, as the condensed heterocycle formed by R ₆₁ and R ₆₂ bonded to each other,
For example, heterocycles such as 1,3-diselenolane and 1,4-diselenan are mentioned.

Examples of the aryl group represented by R ₆₁ and R ₆₂ include a phenyl group and a naphthyl group.

The above-mentioned alkyl group represented by R ₆₁ and R ₆₂ may have a substituent at any position, and specific examples of the substituent include, for example, halogen atom (chlorine atom, bromine atom, fluorine atom). Atom, iodine atom), trifluoromethyl group,
Alkoxy group (eg, unsubstituted alkoxy groups such as methoxy, ethoxy, butoxy, substituted alkoxy groups such as 2-methoxyethoxy, benzyloxy), hydroxyl group, cyano group, aryloxy group (eg, phenoxy, tolyloxy, etc. Substituted or unsubstituted groups), or aryl groups (eg, substituted or unsubstituted groups such as phenyl, m-tolyl, p-chlorophenyl, carboxyphenyl, etc.), styryl groups, heterocyclic groups (eg, furyl, thienyl). Etc.), carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl, etc.), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, etc.), acylamino group (eg, acetyl). Amino, propionylamino, benzoylamino, etc. groups), acyl groups (eg If acetyl, each group of benzoyl), an alkoxycarbonyl group (e.g., groups such as ethoxycarbonyl), a sulfonamido group (e.g., methanesulfonamido, each group such as benzenesulfonamide),
A sulfonyl group (for example, each group such as methanesulfonyl, p-toluenesulfonyl, etc.), and a carboxyl group, a sulfo group, or any other group.

[0066] aryl group represented by R ₆₁ and R _62, and even in the fused carbocyclic rings and condensed heterocyclic R ₆₁ and R ₆₂ is formed by bonding to each other have a substituent at any position well, other alkyl group described for R ₆₁ and R _62, include the substituents described as examples of the substituents of R ₆₁ and R _62.

Specific examples of the selenium compound represented by the general formula [6] are shown below, but the compound of the present invention is not limited thereto.

[0068]

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The compound represented by the general formula [6] of the present invention can be obtained by, for example, Journal of the Chemical Society Chemical Communication, page 866 (1
980), 235, 294-295 (1983).
It can be easily synthesized by a conventionally known method described in, for example.

The compounds represented by the above general formulas [1] to [6] of the present invention are water or a solution of a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, phenoxyethanol, etc., alone or as a mixed solvent. Alternatively, it may be added as a fine crystal dispersion at any time during emulsion production, but it is preferably added at the start of chemical ripening.

The addition amount of the compounds represented by the general formulas [1] to [6] of the present invention is not uniform depending on the type of silver halide photographic emulsion and the conditions used, but usually 1 mol of silver halide is used. It is in the range of 3 × 10 ^-8 to 1 × 10 ^-3 mol per mol, and preferably 1 × 10 ^{-7 to} 5 per mol of silver halide.
It is preferably in the range of × 10 ^-4 mol.

In the present invention, chemical sensitization using the compound of the present invention may be combined with generally known sulfur sensitization, reduction sensitization and noble metal sensitization methods.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used in addition to the sulfur compounds contained in gelatin.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

Examples of the reduction sensitizer include stannous salt, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

In the present invention, the halogen composition of silver halide in the silver halide emulsion is pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or chloroiodo containing 60 mol% or more of silver chloride. It is silver bromide.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 μm to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CEM).
ees & T. H. James: The theory
of the photographic process
ss), 3rd edition, pp. 36-43 (1966 (published by Macmillan “Mcmilllan”)).

The shape of the silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
A so-called monodisperse emulsion containing 0%, preferably 95%, is preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

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 of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion include cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt and ruthenium salt in at least one of the grain forming process and the growing process. It is preferable to add an osmium salt or a complex salt containing these elements.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

As the hydrazine compound of the present invention, a compound represented by the following general formula [H] is used.

The general formula [H] will be described in detail below.

[0085]

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In the formula, A ₀ represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by A ₀ is preferably one having 1 to 30 carbon atoms, particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. Examples thereof include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, a benzyl group, and the like. These are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

The aromatic group represented by A ₀ in the general formula [H] is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A ₀ in the general formula [H] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen. , Imidazole ring, tetrahydrofuran ring, morpholine ring, pyridine ring, pyrimidine ring, quinoline ring, thiazole ring, benzothiazole ring, thiophene ring and furan ring.

Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group represented by A ₀ preferably have a substituent. Preferred substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, Alkylthio group, arylthio group, sulfothio group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide Examples thereof include a group, a carboxy group and a phosphoric acid amide group, and these groups may be further substituted.

Among these substituents, a pH of 9.0 or higher and 1
Using a developing solution of 0.5 or less, the total processing time (Dry to
When Dry) is treated for 60 seconds or less, a substituent having an acidic group with a pKa of 7 to 11 is preferable, and specific examples thereof include a sulfonamide group, a hydroxy group, and a mercapto group, and particularly preferable sulfonamide. Groups.

A ₀ preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in a non-moving photographic additive such as a coupler is preferable, and as the ballast group, an alkyl group or an alkenyl group having 8 or more carbon atoms and relatively inert to photographic properties is preferable. , An alkynyl group, an alkoxy group,
Examples thereof include a phenyl group, a phenoxy group and an alkylphenoxy group.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

B ₀ represents a blocking group, preferably -G ₀ -D ₀ G ₀ is -CO- group, -COCO- group, -CS- group, -C.
(= NG ₁ D ₁₎ - represents a group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 1 D} 1). G ₁ represents a simple bond, —O— group, —S— group or —N (D ₁ ) — group, D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, When a plurality of D _1's are present, they may be the same or different.

D ₀ is an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, and a mercapto group.

Preferred G ₀ is --CO-- group, --C
An OCO- group, particularly preferably a -COCO- group is mentioned.

Preferred D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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The preferred pyridinium compound of the present invention is represented by the following general formula [Pa], [Pb] or [Pc].

[0105]

[Chemical 21]

In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a non-metal atom group for completing the nitrogen-containing heterocycle,
It may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. The heterocycle composed of A ¹ , A ² , A ³ , A ⁴ and A ⁵ may have a substituent and may be the same or different. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group,
Alkynyl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group,
Carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group, arylthio group Represent A preferred example is A
¹ , A ² , A ³ , A ⁴ and A ⁵ can be a 5- or 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, etc.), and more preferable examples Examples thereof include a pyridine ring.

B _p represents a divalent linking group. The divalent linking group means alkylene, arylene, alkenylene, -S
_{O 2 -, - SO -,} - O -, - S -, - CO -, - N
(R ₆₎ - (R ₆ is an alkyl group, an aryl group, a hydrogen atom) represents what is configured alone or in combination. Preferred examples of B _p include alkylene and alkenylene.

R ¹ , R ² and R ⁵ represent an alkyl group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituent mentioned as the substituent of A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

As a preferred example, R ¹ , R ² and R ⁵ each represent an alkyl group having 4 to 10 carbon atoms. A more preferred example is a substituted or unsubstituted aryl-substituted alkyl group. X _p represents a counter ion required to balance the charge of the entire molecule. For example, they represent chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, and oxalate. n _p represents the number of counterions required to balance the charge of the entire molecule, and in the case of an intramolecular salt, n _p is 0.

Specific examples of the pyridinium compounds represented by the above general formulas [Pa], [Pb] and [Pc] are shown below, but the present invention is not limited to these.

[0111]

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[0112]

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[0113]

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[0114]

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[0115]

[Chemical formula 26]

In the present invention, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb] in order to effectively promote the contrast increase by the hydrazine derivative and the pyridinium compound.

[0117]

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In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
And R ₁₄ may be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific examples of the nucleation accelerator [Na] and the general formula [Nb] are shown below.

[0121]

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[0122]

[Chemical 29]

[0123]

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[0124]

[Chemical 31]

[0125]

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The tetrazolium compound of the present invention is preferably represented by the following general formula [T].

[0127]

[Chemical 33]

In the present invention, the substituents R ₁ , R ₂ and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T] are hydrogen atoms or Hammett's sigma value (σP) showing electron withdrawing degree. ) Is preferably negative.

Hammett's sigma value for phenyl substitution is well documented, for example, Journal of Medical Chemistry.
Chemistry) Volume 20, page 304, 1977
Year, C. As a group having a particularly preferable negative sigma value, such as a methyl group (σP = −0.17,
All numerical values in parentheses below indicate σP values), ethyl groups (-0.15), cyclopropyl groups (-0.21),
n-propyl group (-0.13), iso-propyl group (-
0.15), cyclobutyl group (-0.15), n-butyl group (-0.16), iso-butyl group (-0.2
0), n-pentyl group (-0.15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-0.3
7), a methoxy group (-0.27), an ethoxy group (-0.
24), propoxy group (-0.25), butoxy group (-
0.32), a pentoxy group (-0.34) and the like, all of which are useful as a substituent of the compound of the general formula [T].

N represents 1 or 2, and examples of the anion represented by X _T ^n- are halogen ions such as chloride ion, bromide ion and iodide ion, inorganic acids such as nitric acid, sulfuric acid and perchloric acid. Acid radicals, organic acid radicals such as sulfonic acid and carboxylic acid, anionic activators, specifically, lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion and higher alkylbenzenes such as p-dodecylbenzene sulfonate anion. Higher alkyl sulfate ester anions such as sulfonate anion and lauryl sulfate anion, borate anions such as tetraphenylboron, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anion, and cetyl polyethenoxy sulfate anions. Polyether alcohol Ester anion, higher aliphatic acid such as stearic acid anion anion, those with a acid radical in a polymer of polyacrylic acid anion, and the like.

Specific examples of the compound represented by formula [T] are shown below, but the tetrazolium compound is not limited thereto.

[0132]

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The above tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, Volume 55, pp. 335-483.

The tetrazolium compound represented by the general formula [T] may be used alone or in combination of two or more kinds at an appropriate ratio.

The hydrazine compound, pyridinium compound, nucleation accelerator or tetrazolium compound used in the present invention can be used in any layer on the silver halide emulsion layer side, but is preferably silver halide. It is preferably used in the emulsion layer or its adjacent layer. The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

The light-sensitive material of the present invention is processed using an automatic developing machine having a developing tank, a fixing tank and a washing tank or a stabilizing tank. At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material. The developing replenishing amount and the fixing replenishing amount are preferably 30 ml or more and 300 ml or less per 1 m ² in order to reduce the amount of waste liquid, and more preferably 75 to 200 ml per 1 m ² .

In order to shorten the developing time, the present invention provides a total processing time (Dry to Dry) of 10 days from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when the processing is performed using the automatic developing machine. ~ 60 seconds. The total processing time referred to here includes the total process time required for processing the black and white photosensitive material, and specifically includes the steps required for the processing, such as development, fixing, washing, stabilizing, and drying. It is the time including all the time, that is, the time of Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 15 to 50 seconds.

In the automatic processor, a heat transfer material at 90 ° C. or higher (for example, a heat roller at 90 ° C. to 130 ° C.) or a radiation object at 150 ° C. or higher (for example, tungsten, carbon, nichrome, zirconium oxide / yttrium oxide /
Infrared rays are emitted from a mixture of thorium oxide, silicon carbide, etc. by directly passing an electric current to generate heat, or by transmitting heat energy from a resistance heating element to a radiator such as copper, stainless steel, nickel or various ceramics to generate heat. It is preferable to include those having a zone for drying in).

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

Specifically, Research Disclosure Vol. 176, RD-17643 (December 1978), pp. 2-3, US Pat. Nos. 4,425,425 and 4,42.
No. 5,426 can be used. The sensitizing dye may be dissolved by using ultrasonic vibration described in U.S. Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention and adding it to an emulsion, US Pat. No. 3,482,981
Nos. 3,585,195 and 3,469,987
Nos. 3,425,835 and 3,342,605
No., British Patent Nos. 1,271,329 and 1,038,0
29, 1,121,174, U.S. Pat. No. 3,66.
Nos. 0,101 and 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Re
search Disclosure) Volume 176 176
43 (issued December 1978), page 23, IV, paragraph J.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example triazain Dens, tetrazaindenes (especially 4-
Hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes, etc .; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds can be added.

The silver halide photographic emulsion and the non-photosensitive hydrophilic colloid used in the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide]
Etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazoles, dialdehyde starch, 2-chloro-6- Hydroxytriazinylated gelatin and the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer used in the present invention have various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. In the above, various known surfactants may be used.

As the binder or protective colloid of the silver halide photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The silver halide photographic emulsion used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate,
(Meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfo A polymer having a combination of alkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

Various other additives are used in the light-sensitive material of the present invention. For example, desensitizers, plasticizers, slip agents,
Examples include development accelerators and oils.

Regarding these additives and the above-mentioned additives, specifically, Research Disclosure 176
Nos. (Described above), pages 22 to 31, etc. can be used.

In the light-sensitive material of the present invention, the emulsion layer and the protective layer may be a single layer or multiple layers composed of two or more layers.
In the case of a multilayer, an intermediate layer or the like may be provided therebetween.

In the light-sensitive material of the present invention, a silver halide photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Those useful as the flexible support include films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and polyethylene terephthalate.

The light-sensitive material of the present invention may contain various dyes for the purpose of improving safety of safelight. Preferred dyes include those represented by the following general formulas (1) to (6).

[0152]

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In the formula, A and A'may be the same or different.
May each represent an acidic nucleus, Q is an aryl group or
Represents a heterocyclic group, B represents a basic nucleus, and B ′ represents a heterocyclic group.
And X and Y may be the same or different,
Each represents an electron-withdrawing group, L ₁, L₂And L_ThreeAre each
Represents a methine group. m represents 0 or 1, n is 0, 1 or
Or 2 and p represents 1 or 2. However, the general formula
The dyes represented by (1) to (6) are carboxy in the molecule.
Group, sulfonamide group and sulfamoyl group
Has at least one group.

Examples of the aryl group represented by Q in the above general formulas (1) and (4) include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by Q include pyridine, quinoline, isoquinoline, pyrrole, pyrazole, imidazole and indole residues.

The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfamoyl group and a sulfonamide group, and two or more of these substituents may be combined. Preferably,
Alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, 2-hydroxyethyl group, etc.), hydroxy group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, methylenedioxy group, 2-hydroxyethoxy group,
n-butoxy group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-
Ethyl-N-methanesulfonamide ethylamino group, morpholino group, piperidino group, pyrrolidino group etc.), carboxy group, sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), sulfamoyl group (eg sulfamoyl group, methyl (Sulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The acidic nuclei represented by A and A'in the general formulas (1), (2) and (3) are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin and thio. Hydantoin, oxazolone,
Examples thereof include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and pyrazolopyridone.

The basic nucleus represented by B in the general formulas (3) and (5) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Examples thereof include thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole and indole.

The electron withdrawing groups represented by X and Y in the general formulas (4) and (5) may be the same or different, and for example, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carboxy group, acyl group, alkylsulfonyl group, arylsulfonyl group,
A sulfamoyl group is mentioned.

The heterocycle represented by B'in the general formula (6) is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

L ₁ , L ₂ and L _{3 of the} general formulas (1) to (5)
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isobutyl, etc.),
Aryl groups (eg phenyl, p-tolyl, p-chlorophenyl etc.), alkoxy groups having 1 to 4 carbon atoms (eg methoxy group, ethoxy group etc.), aryloxy groups (eg phenyl group etc.), aralkyl groups (eg benzyl) Group, phenethyl group, etc.), heterocyclic group (eg, pyridyl, furyl, thienyl, etc.), substituted amino group (eg, dimethylamino, tetramethyleneamino, anilino, etc.), alkylthio group (eg, methylthio group, etc.).

Next, specific examples of the dyes preferably used in the present invention will be given.

[0162]

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[0163]

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[0164]

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[0165]

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[0166]

[Chemical 40]

[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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These dyes contain at least one dissociative proton having a pKa in the range of 4 to 11, preferably 4.5 to 7.0 in a mixed solvent of water-ethanol volume ratio of 1: 1. To have. Further, in the present invention, the immobilization can be achieved by the silver salt and the silver complex formed by the reaction of the dye and the silver ion. Preferred dyes capable of forming silver salts of such dyes are, for example, JP-A-5-18123.
No. 0 General formula [I] described on pages 4 to 28
Examples thereof include compounds represented by [V], general formulas [I ′] to [V ′], and general formula [VI]. Further, specific compounds are described in I-1 to 3 described on page 6 to page 46 of the same specification.
7, II-1 to 5, III-1 to 7, IV-1 to 6, V-1 to
5, I'-1 to 12, II'-1 to 9, III'-1 to 9, I
V'-1 to 9, V'-1 to 6, and VI-1 to 52.

In the present invention, the above general formulas (1) to
The method of dispersing the dye represented by (6) is not particularly limited, but a known method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied.

The average particle size of the finely dispersed dye fine particles preferably used in the present invention can be any value,
The thickness is preferably 0.01 to 20 μm, more preferably 0.03 to 2 μm. Further, the variation coefficient of the particle diameter of the finely dispersed dye particles of the present invention is preferably 60.
% Or less, and more preferably 40% or less.

The layer containing the fine dye particles of the present invention is provided between the emulsion layer and the support. Preferably, the first undercoat layer is provided on the support, and the hydrophilic colloid second undercoat layer containing the dye fine particles of the present invention is provided thereon. The addition amount of the fine dye particles of the present invention is not particularly limited, but the addition amount is preferably such that the effective transmission density is 0.3 or more and 2 or less.

The hydrophilic colloid layer containing fine dye particles preferably used in the present invention has a coating amount of 0.05 g / m 2.
Is preferably less than ² or more 0.5 g / m ^2, more preferably less than 0.18 g / m ² or more 0.42 g / m ^2. Further, in order to further enhance the effect of the present invention, it is preferable that the ratio of the average particle size of the dye fine particles to the film thickness of the dye layer is 0.2 to 2.0.

The developing agents that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone). 3-pyrazolidones (eg 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol,
Ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino (Phenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.), transition metal complex salts (T
A complex salt of a transition metal such as i, V, Cr, Mn, Fe, Co, Ni, Cu, etc. These may have a reducing power in order to be used as a developing solution. For example, Ti ³⁺ , V ²⁺ ,
It takes the form of a complex salt such as Cr ²⁺ , Fe ^2+, etc.
Examples include aminopolycarboxylic acids and salts thereof such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), and phosphoric acids and salts thereof such as hexametapolyphosphoric acid and tetrapolyphosphoric acid. ) And the like can be used alone or in combination, but a combination of 3-pyrazolidones and ascorbic acid,
A combination of aminophenols and ascorbic acid, 3-
It is preferable to use a combination of pyrazolidones and a transition metal complex salt and a combination of aminophenols and a transition metal complex salt.

Further, the developing agent used in the present invention preferably does not use hydroquinones.

The developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844,
4-26838, 4-362942, 1-3
Examples thereof include compounds described in No. 19031.

The developing waste liquid can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

If necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) may be added to the developer. , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitropentindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (for example, US Pat. No. 2,304,
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. Total processing time (Dry to Dry) is 6
The pH of the developer is 8.5 to 10.5 in order to set it to 0 seconds or less.
Is preferably adjusted to

As the fixing solution, those having a generally used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution.

If desired, the fixer may contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid),
Compounds such as a pH adjuster (for example, sulfuric acid) and a chelating agent capable of softening water can be included.

The developer may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a semi-kneaded viscous liquid having high viscosity. Further, it may be used after being diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature can be set in the usual temperature range of 20 to 30 ° C. or in the high temperature processing range of 30 to 40 ° C.

[0192]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) An average thickness of 0.05 mol% silver chloride and the balance of silver bromide was 0.05 using the simultaneous mixing method.
Silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. Add K ₃ RuCl ₆ to 8 per mole of silver when mixing core particles.
× 10 ^-8 mol was added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The emulsion obtained was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.2 mol% silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.25 μm. , The rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Then, JP-A-2-28013
No. 9 described in Japanese Unexamined Patent Publication (Kokai) No. 2-2 (the modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl).
Desalting was carried out using the exemplified compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 190 mv at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion in an amount of 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
The compounds of the present invention and the sulfur compound were added as shown in Table 1 and chemically aged at a temperature of 60 ° C. until the maximum sensitivity was obtained.
After completion of aging, 4-hydroxy-6-methyl-1,3,3a
2 × 10 ⁻³ mol of 7-tetrazaindene and 3 × of 1-phenyl-5-mercaptotetrazole per mol of silver.
10 ^-4 mol and gelatin were added.

(Preparation of silver halide emulsion B) 60 mol% of silver chloride, 1.5 mol% of silver iodide and the rest of silver bromide by the simultaneous mixing method.
5 μm silver chloroiodobromide core grains were prepared. When mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 10 per mol of silver.
^-8 mol was added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion had an average thickness of 0.
10 μm core / shell type monodisperse (variation coefficient 10%) silver chloroiodobromide having an average diameter of 0.42 μm (90 mol% silver chloride,
The emulsion was a tabular grain emulsion composed of 0.2 mol% of silver iodobromide and the rest of silver bromide. Then, the modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-2801)
No. 39, No. 287 (3), Exemplified Compound G-8) was used for desalting. The EAg after desalting was 180 mv at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
The compound of the present invention, the gold compound, and the sulfur compound were added as shown in Table 1 and chemically aged at a temperature of 60 ° C. until the maximum sensitivity was obtained. After completion of aging 4-hydroxy-6-methyl-
1,3,3a7-tetrazaindene is added in an amount of 2 per mole of silver.
× 10 ⁻³ mol, 1-phenyl-5-mercaptotetrazole 3 × 10 ⁻⁴ mol and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative) A gelatin subbing layer of the following Formulation 1 was prepared on a support with a gelatin content of 0.
5 g / m so that the ^2, amount of silver 2.9 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, the amount of gelatin is 1.0
g / m at ^2, the following formulation 3 of the coating solution of gelatin weight of 0.3 g / m ² as a further intermediate protective layer thereon
In addition, a silver halide emulsion layer 2 of Formula 4 was added to the above layer so that the silver amount was 0.2 g / m ² and the gelatin amount was 0.4 g.
/ M such that ^2, further amount of gelatin coating solution having the following formulation 5 is simultaneous multilayer coating so as to be 0.6 g / m ^2.
A backing layer of the following formulation 6 was formed on the opposite side of the undercoat layer so that the amount of gelatin was 0.6 g / m ^2, and a polymer layer of the following formulation 7 was further formed on the backing layer of the formulation 8 below. A sample was obtained by simultaneously coating the backing protective layer with the emulsion layer so that the amount of gelatin was 0.4 g / m ² .

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Dye a (ball-mill dispersed into powder having a particle size of 0.1 μm) 25 mg / m ² Dye b (ball-mill dispersed and particles 20 mg / m ² sodium polystyrene sulfonate 10 mg / m ² S-1 (sodium-iso-amyl-decyl sulfosuccinate) 0.4 mg / m ² Formulation 2 (silver halide) Emulsion Layer 1 Composition) Silver Halide Emulsion A So that the amount of silver is 2.9 g / m ² Sensitizing dye d-1 6 mg / m ² Sensitizing dye d-2 3 mg / m ² Hydrazine derivative As shown in Table 1. Nucleation accelerator 40 mg / m ² Compound e 100 mg / m ² Latex polymer f 1.0 g / m ² Hardener g 5 mg / m ² S-1 0.7 / m ² 2-Mercapto-6-hydroxypurine 10 mg / m ² EDTA 50 mg / m ² formulation 3 (intermediate layer composition) gelatin 0.3 g / m ² S-1 2 mg / m ² formulation 4 (silver halide emulsion layer 2 composition) silver halide emulsion B silver amount 0.2 g / the sensitizing dye to be ^{m 2 d-1 0.5mg / m} 2 redox compound ^{RE-1 4mg / m 2 S} -1 1.7mg / m 2 formulation 5 (emulsion protective layer composition) gelatin 0.6 g / m ² Dye c (ball mill-dispersed powder having a particle size of 0.1 μm) 40 mg / m ² S-1 12 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 25 mg / m ² 1, 3-Vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Hardener j 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² compound i 100 mg / m ² prescription 7 (polymer layer composition) latex j (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² hardener g 6 mg / m ² prescription 8 (backing protective layer) gelatin 0.4 g / m ² matting agent: monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant h 1 mg / m ² dye k 20 mg / m ² after performing exposure wavelength 670nm as a substitute characteristic of _{H- (OCH 2 CH 2) 68} -OH 50mg / m 2 hardener g 20 mg / m ² obtained sample was in close contact with a step wedge red semiconductor laser, Processing was performed under the following conditions using an automatic processor for rapid processing (manufactured by GR-26SR Konica Co., Ltd.) using a developing solution and a fixing solution having the following compositions. In addition, in order to evaluate the fine dot quality, SG-747RU manufactured by Dainippon Screen Co., Ltd.
The same treatment was performed after exposure with halftone dots (FM screen) having a random pattern of 6 μm. 1m film
While replenishing 120 ml of developer and fixer per ² days, 100 sheets of large size film with 80% of the area blackened per day were processed and run for 8 days for a total of 8
00 sheets were processed. The performance before running and after 800 sheets of running were compared.

(Developer Composition) Concentrated Developer Formula A Diethyltriamine pentaacetic acid / 5 sodium salt 9 g / l Compound A-17 0.6 mol / l Sodium sulfite 0.45 mol / l 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone 7 g / l potassium carbonate 2.4 mol / l 5-methylbenzotriazole 0.75 g / l potassium bromide 22 g / l boric acid 6 g / l diethylene glycol 80 g / l compound 1-7 0.3 g / L KOH was added in an amount such that the working solution had a pH of 10.0.

At the time of use, 2 parts of water was added to 1 part of the concentrated developer A to prepare a working solution. This used solution was used as a developing mother solution and a developing replenishing solution.

(Fixing solution composition) Concentrated fixing solution A Ammonium thiosulfate (70% aqueous solution) 400 ml / l Sodium sulfite 45 g / l Boric acid 20 g / l Sodium acetate trihydrate 70 g / l Acetic acid (90% aqueous solution) 30 g / l Tartaric acid 6 g / l Glutaraldehyde 6 g / l Aluminum sulfate (27% aqueous solution) 50 ml / l Sulfuric acid was adjusted so that the pH of the used solution was 4.9.

At the time of use, 1 part of water was added to 1 part of the concentrated fixing solution A to prepare a working solution. This used solution was used as a fixing mother liquor and a fixing replenisher.

(Processing conditions) (Process) (Temperature) (Time) Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing 40 ° C. 10 seconds Drying 50 ° C. 12 seconds Total 44 seconds

[0204]

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[0205]

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[0206]

[Chemical 51]

[0207]

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[0208]

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[0209]

[Table 1]

(Evaluation of Sensitivity and Gamma) The obtained developed sample was measured with PDA-65 (Konica Digital Densitometer). The sensitivities in the table are sample No. The sensitivity was expressed as a relative sensitivity when the sensitivity at a density of 3.0 was set to 100. Further, gamma is represented by tangents of densities of 0.1 and 3.0. If the gamma value in the table is less than 7, it cannot be used, and if it is 7 or more and less than 10, it is still insufficient. When the gamma value is 10 or more and 30 or less, a super-high contrast image can be obtained, and it is shown that the photosensitive material is sufficiently practical.

(Evaluation of Fog) The unexposed portion of the obtained developed sample was measured with PDA-65 (Konica Digital Densitometer).
It was measured at. A value of 0.06 or more is a level that cannot be practically used.

(Evaluation of Black Spots) The obtained developed sample was visually evaluated using a magnifying glass of 100 times, and was classified into 5 grades of 5, 4, 3, 2, 1 in the order of less black spots. It was ranked. Ranks 1 and 2 are levels that are not practically desirable.

(Evaluation method of halftone dot quality) SG-747RU
16μ random pattern halftone dot (FM screen)
The halftone dot quality (sharpness) was evaluated by using a magnifying glass 100 times the midpoint (target 50%) of the light exposed in (1). The highest rank was set to 5, and the rank was lowered to 4, 3, 2, and 1 according to the halftone dot quality and evaluated. Ranks 1 and 2 are levels that are not practically desirable.

Table 2 shows the evaluation results.

[0215]

[Table 2]

It can be seen that the samples of the present invention have high sensitivity, small fog, and few black spots. Further, even when a large amount of sample is rapidly processed by reducing the replenishing amount of the developing solution and the replenishing amount of the fixing solution with an automatic developing machine, fluctuations in sensitivity, increase in fog and deterioration of black spots are small, It can be seen that even when dots are reproduced, there are few problems such as deterioration of dot quality and deterioration of dot reproducibility.

Example 2 (Preparation of Silver Halide Emulsion C) 8 × 10 K ₃ Os (H ₂ O) Cl ₅ was added per 1 mol of silver at the time of mixing using the simultaneous mixing method.
^-5 moles and K ₂ IrCl ₆ at 3 × 10 ^-7 per mole of silver
After adding mol and desalting by a conventional method, the average particle size is 0.10 μm.
An emulsion of monodisperse (variation coefficient 10%) cubic chlorobromide (99 mol% silver chloride, the rest consisting of silver bromide) cubic grains was obtained.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene, potassium bromide and citric acid were added to the obtained emulsion to give compounds of the present invention or sulfur compounds as shown in Table 3. After the addition, chemical aging was carried out at a temperature of 60 ° C. until the maximum sensitivity was obtained. After completion of aging 4-hydroxy-6
-Methyl-1,3,3a7-tetrazaindene and 1-
Phenyl-5-mercaptotetrazole (3 × 10 ^-4 mol) and gelatin were added.

(Preparation of silver halide photographic light-sensitive material containing tetrazolium compound for photolithography in bright room) A gelatin subbing layer having the following Formulation 9 was prepared on a support to give a gelatin content of 0.5 g / m ² . Then, a silver halide emulsion layer of Formulation 10 was applied thereon so that the amount of silver was 2.8 g / m ² and the amount of gelatin was 1.0 g / m ^2, and the following formulation 11 was applied as a protective layer on the upper layer. The amount of gelatin is 0.5 g /
and simultaneous multi-layer coating so as to be m ^2. Further, on the undercoat layer on the opposite side, JP-A-5-188518, 360 (14) to 3
Example 1 on page 61 (15) After coating the conductive layer, a backing layer having the following formulation 12 was coated with a gelatin amount of 0.4.
such that g / m ^2, the polymer layer having the following formulation 13 thereon, further that the amount of gelatin backing protective layer having the following formulation 14 thereon is simultaneous multilayer coating so that 0.4 g / m ² A sample was obtained.

Formulation 9 (gelatin undercoat layer composition) Gelatin 0.6 g / m ² Dye b (ball mill dispersed into powder having a particle size of 0.1 μm) 20 mg / m ² Dye c (ball mill dispersed into particles Powder having a diameter of 0.1 μm) 10 mg / m ² Styrene-maleic acid copolymer hydrophilic polymer (thickener) 10 mg / m ² S-1 (sodium-iso-amyl-decylsulfosuccinate) 0.4 mg / m ² Formulation 10 (silver halide emulsion layer composition) Silver halide emulsion C To obtain a silver amount of 2.8 g / m ² Tetrazolium compound As shown in Table 3, sodium dodecylbenzenesulfonate 10 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound M 6 mg / m ² latex polymer f 1.0 g / m ² hardener g 40 mg / m ² S-1 0.7 mg / m ² styrene -Hydrophilic polymer of maleic acid copolymer (thickener) 20 mg / m ² Formulation 11 (emulsion protective layer composition) Gelatin 0.5 g / m ² Dye c (ball mill-dispersed into powder having a particle size of 0.1 μm) 100 mg / m ² S-1 12 mg / m ² Matting agent: monodisperse silica having an average particle size of 3 μm 15 mg / m ² Matting agent: monodisperse silica having an average particle size of 8 μm 20 mg / m ² 1,3-vinylsulfonyl 2-Propanol 50 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Formulation 12 (backing layer composition) Gelatin 0.4 g / m ² S-1 5 mg / m ² latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05 .mu.m) 70 mg / m ² styrene-hydrophilic polymer maleic acid copolymer (thickener) 20 mg / m ² Compound i 100 mg / m ² formulation 13 (Polymer Layer Composition) latex n (styrene: butadiene: acrylic acid = 30: 65: 5) 1.0g / m 2 hardener g 10 mg / m ² formulation 14 (backing protective layer ) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² H- (OCH ₂ CH ₂₎ a ₆₈ -OH 50mg / m ² hardener j 40 mg / m ² obtained sample is subjected to exposure in close contact with a step wedge bright room printer P-627GM (manufactured by Dainippon screen) When the total processing is performed by modifying the automatic processor SRX-1001 (manufactured by Konica Corp.) using the developer and fixer having the following composition to change the line speed. (Dry to
Dry) was processed for 30 seconds (development temperature 38 ° C.). In addition, as a substitute evaluation of storability with time, the sample was tested at 55 ° C and 48%
The same treatment as described above was performed after leaving the sample in an RH atmosphere for 3 days to forcibly deteriorate it.

(Developer composition) Amount per 1 liter of used solution Developer formulation B Ammonia water (25%) 50 ml Diethylamine 5 acetic acid / 5 sodium 0.15 mol Sodium sulfite 20 g Boric acid 8 g Potassium bromide 15 g Potassium carbonate 40 g Compound 1-7 60 mg diethylene glycol 40g Benz triazole _{0.2g FeSO 4 (NH 4) 2} SO 4 · 6H 2 O 0.15 moles of 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.9g potassium hydroxide Aqueous solution pH 9.2 (Fixing liquid composition) Amount per 1 liter of used liquid Fixing liquid formulation B Sodium thiosulfate 100 g / liter Sodium sulfite 22 g / liter Boric acid 10 g / liter Sodium acetate trihydrate 34 g / liter Tartaric acid 3. 0 g To adjust the pH of the working solution to 7.5 with l glutaraldehyde bisulfite adduct 0.1 mol / l acetic acid.

The evaluation was carried out by measuring the sensitivity of the sample No. 14 concentrations 3.
The sensitivity, gamma, and fog were evaluated in the same manner as in Example 1 except that the relative sensitivity when the sensitivity at 0 was 100 was used. The results are shown in Table 4.

[0223]

[Table 3]

[0224]

[Table 4]

It can be seen that the samples of the present invention are excellent in high sensitivity, small fog and excellent in comparison with the comparison. Further, it can be seen that the sample of the present invention is excellent in the fluctuation of sensitivity, the softening of the image and the increase of fog even in the evaluation of the storage stability over time.

Example 3 A sample was prepared in the same manner as in Example 1 except that pyridium compounds P-3, P-6 and P-13 were used in place of the hydrazine derivative in Example 1, and the same procedure as in Example 1 was performed. As a result of the evaluation of 1., the same results as in Example 1 could be obtained.

[0227]

The black-and-white silver halide photographic light-sensitive material and the processing method thereof according to the present invention enable rapid processing and low replenishment processing, high sensitivity and small fog, less black spots, and further fatigue of the processing solution. It is possible to obtain an excellent image with little deterioration in photographic performance even after storage with time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 5/31 G03C 5/31

Claims (7)

[Claims] 1. A silver halide emulsion layer on a support,
The silver halide emulsion contains 60 mol% or more and 100% or less of silver chloride, and the silver halide emulsion has the following general formula [1].
A black-and-white silver halide photographic light-sensitive material, which is chemically sensitized with at least one compound selected from [6]. Embedded image [In the general formula [1], R ₁₁ , R ₁₂ and R ₁₃ each represent an aliphatic group, an aryl group or a heterocyclic group, and R ₁₁ and R ₁₂ are bonded to each other to form a carbocycle or a heterocycle. You may form. X ₁₁ represents a selenium atom or a tellurium atom. R in the general formula [2]
₂₁ , R ₂₂ and R ₂₃ are each an alkyl group, an aryl group,
Represents a heterocyclic group. In formula [3], R ₃₁ and R ₃₂ each represent an alkyl group, an aryl group, or a heterocyclic group. In the general formula [4], R ₄₁ and R ₄₂ each represent an alkyl group, an aryl group, or a group which forms a heterocycle with X ₄₁ by combining between R ₄₁ and R _42, and Ar is Represents an aryl group. X
₄₁ represents a selenium atom or a tellurium atom, W represents a sulfonyl group or a carbonyl group, and n represents an integer of 0 or 1. In the general formula [5], R ₅₁ , R ₅₂ , R ₅₃ and R
₅₄ represents an alkyl group or an aryl group, and X ₅₁ represents an oxygen atom or a sulfur atom. In the general formula [6], R ₆₁ and R
₆₂ is an alkyl group, an aryl group, or R ₆₁ and R _{62, respectively.}
And a group forming a condensed carbocycle or a condensed heterocycle by being bonded to each other. ] 2. A silver halide emulsion layer is provided on a support,
At least one layer selected from the silver halide emulsion layer and / or its adjacent layer contains a hydrazine derivative, and the silver halide emulsion is chemically enhanced with at least one compound selected from the above formulas [1] to [6]. A black-and-white silver halide photographic light-sensitive material characterized by being perceived. 3. A silver halide emulsion layer is provided on a support,
At least one layer selected from the silver halide emulsion layer and / or its adjacent layer contains a pyridinium compound, and the silver halide emulsion is chemically enhanced with at least one compound selected from the above general formulas [1] to [6]. A black-and-white silver halide photographic light-sensitive material characterized by being perceived. 4. A silver halide emulsion layer on a support,
At least one layer selected from the silver halide emulsion layer and / or its adjacent layer contains a tetrazolium compound,
A black and white silver halide photographic light-sensitive material characterized in that the silver halide emulsion is chemically sensitized with at least one compound selected from the above formulas [1] to [6]. 5. When processed by an automatic processor for black and white silver halide photographic light-sensitive materials having a developing tank, a fixing tank and a washing tank or a stabilizing tank, the replenishing amount of development and the replenishing amount of fixing are respectively 30.
5. The method for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the processing is carried out while replenishing with an amount of from ml / m ^{2 to} 300 ml / m ² . 6. An automatic developing machine for a black-and-white silver halide photographic light-sensitive material comprising the black-and-white silver halide photographic light-sensitive material according to claim 1, 2, 3 or 4, which has a developing tank, a fixing tank and a washing tank or a stabilizing tank. In the processing, the total processing time (Dry to Dry) from the insertion of the film tip of the photosensitive material into the automatic developing machine to the exit from the drying zone is 10 seconds or more and 60 seconds or less. Black and white silver halide photographic light-sensitive material processing method. 7. The method of processing a black-and-white silver halide photographic light-sensitive material according to claim 5 or 6, wherein the processing is carried out with a developing solution containing no hydroquinone.