JPH06337492A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material which has a high sensitivity and a hard tone even though it is treated with a developer having a relative low pH, by adding a specific compound into a silver halide emulsion layer or a hydrophilic colloid layer. CONSTITUTION:At least one silver halide emulsion layer and/or another hydrophilic colloid layer are formed on a substrate, and hidrazine derivative and a nucleus formation accelerator are added to these layers. Further, the sliver halide emulsion layer and/or the hydrophilic colloid layer contain a compound given by the expression where Z is a group of atoms necessary for completing thiazolin nucleus, selenazolin nucleus or the like, Q is a group of atoms necessary for completing rhodanin nucleus, 2-thiooxazolin-2, 4-dion nucleus, 2-thiohydantoin nucleus or the like. Further, R1 and R2 are hydrogen atoms, substituted or unsubstituted alkyl group or the like, and P is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an ultrahigh-contrast silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle diameter of 0.2 μm, a narrow particle distribution and a well-shaped particle shape, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion.
By treating this lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, a high contrast,
Images with high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
It is difficult to keep the development quality constant during continuous use. There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in JP-A-56-106244, a silver halide photographic light-sensitive material containing a hydrazine derivative is treated with an alkali developing solution. According to these methods, it is possible to obtain a high-contrast image even by processing with a developer which has good preservative property and can be processed rapidly.

In these techniques, in order to fully exert the high contrast property of the hydrazine derivative, it was necessary to perform processing with a developing solution having a pH of 11.2 or higher. pH 11.2 or higher
In the pH developing solution, the developing agent is easily oxidized when exposed to air.
It is more stable than the lith developer, but due to the oxidation of the developing agent, an ultrahigh contrast image may not be often obtained.

In order to compensate for this drawback, Japanese Patent Laid-Open No. 1-179939
And JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorbing group for a silver halide emulsion grain and a nucleating agent also having an adsorbing group is used to develop at a pH of 11.0 or less. A processing method of developing with a liquid is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if it exceeds a certain limit, the photosensitivity may be impaired, the development may be suppressed, or the action of other useful adsorptive additives may be hindered. Therefore, the amount used is limited, and sufficient hardness cannot be found. Japanese Unexamined Patent Publication (Kokai) No. 5-61144 also discloses a silver halide photographic light-sensitive material containing hydrazine and a nucleation accelerator. However, even with this light-sensitive material, a developer having a pH of 11 or less causes a decrease in sensitivity and a softening tone. There is.

[0007]

In contrast to the problems described above, the object of the present invention is to obtain high sensitivity, high contrast and low density even when processed with a developer having a relatively low pH (11.0 or less). The object is to provide a silver halide photographic light-sensitive material.

[0008]

The above object of the present invention is to provide at least one silver halide emulsion layer and / or other hydrophilic colloid layer on a support, and the silver halide emulsion layer and / or other hydrophilic colloid layer. Alternatively, in a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator in the hydrophilic colloid layer, the silver halide emulsion layer and / or the hydrophilic colloid layer may have the above-mentioned general formula [1] Or [2] (chemical formula 2)
Alternatively, it is achieved by a silver halide photographic light-sensitive material characterized by containing any of the compounds represented by [3] (Chemical Formula 3).

The present invention will be specifically described below.

The hydrazine derivative used in the present invention is described, for example, in Japanese Patent Application No. 5-043861 on page 7 to page 19, and specific compounds are described on page 12 to page 18. The mentioned H-1 to H-40 can be mentioned.

Further, the nucleation accelerator preferably used when the hydrazine derivative is used is described on pages 21 to 27 of the same specification, and specific compounds are described on the same page.
2-1 to 3-6 described on pages 23 to 27 are mentioned.

The compounds represented by the general formulas [1] to [3] will be described in detail.

Here, R ₁ in the general formulas [1] to [3],
The alkyl groups represented by R ₂ , R ₇₁ , R ₇₂ , R ₉₁ , and R ₉₂ include unsubstituted and substituted alkyl groups, and the unsubstituted alkyl group preferably has 18 or less carbon atoms, particularly 8 or less carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, and an n-octadecyl group. The substituted alkyl group preferably has 6 or less carbon atoms in the alkyl portion, and particularly preferably has 4 or less carbon atoms. For example, an alkyl group substituted with a sulfo group (a sulfo group is They may be bonded via an alkoxy group, an aryl group, etc. For example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- (3-sulfopropoxy) ethyl group, 2 -〔2- (3
-Sulfopropoxy) ethoxy] ethyl group, 2-hydroxy
-3-sulfopropyl group, p-sulfophenethyl group, p-sulfophenylpropyl group, etc.) Alkyl group substituted with a carboxy group (carboxy group may be bonded via an alkoxy group, an aryl group, etc.). , Carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, etc.), hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, etc.), acyloxyalkyl Groups (eg 2-
Acetoxyethyl group, 3-acetoxypropyl group, etc.),
Alkoxyalkyl group (for example, 2-methoxyethyl group,
3-methoxypropyl group, etc.), alkoxycarbonylalkyl group (eg, 2-methoxycarbonylethyl group,
3-methoxycarbonylpropyl group, 4-ethoxycarbonylbutyl group, etc.), vinyl group-substituted alkyl group (eg allyl group), cyanoalkyl group (eg 2-cyanoethyl group), carbamoylalkyl group (eg 2-carbamoylethyl group) Etc.), an aryloxyalkyl group (for example,
2-phenoxyethyl group, 3-phenoxypropyl group, etc., aralkyl group (eg, 2-phenethyl group, 3-phenylpropyl group, etc.), or aryloxyalkyl group (eg, 2-phenoxyethyl group, 3-phenoxypropyl group) Etc.) and so on.

[0014] X ₇ ^- as an acid anion represented by, for example chloride, bromide, iodide, methyl sulphate, ethyl sulphate or p- toluenesulfonate ions. n represents 0 or 1, and n represents 0 when the dye forms an inner salt.

Z ₇₁ , Z ₇₂ and Z in the general formulas [1] to [3],
The heterocycle formed by Z ₉ may be substituted with at least one substituent, and as the substituent, a halogen atom (eg, fluorine, chlorine, bromine, iodine), a nitro group, an alkyl group (preferably having a carbon number) 1-4, such as methyl group, ethyl group, trifluoromethyl group, benzyl group, phenethyl group), aryl group (eg phenyl group), alkoxy group (preferably having 1 to 4 carbon atoms, eg methoxy group, Examples thereof include an ethoxy group, a propoxy group, a butoxy group), a carboxyl group, an alkoxycarbonyl group (preferably having 2 to 5, for example, an ethoxycarbonyl group), a hydroxy group, a cyano group and the like.

Regarding Z ₇₁ and Z ₇₂ , examples of the benzothiazole nucleus include benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6- Methoxybenzothiazole, 5-ethoxybenzothiazole, 5-propoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-
Methylbenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, and the like, as the naphthothiazole nucleus, for example, naphtho [2,1-d] thiazole, Naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho Examples of benzoselenazole nuclei include [2,3-d] thiazole and the like, for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-ethoxybenzoselena Zole, 5-hydroxybenzoselenazole, 5-chloro-6-methylbenzoselenazole, and the like, and examples of the naphthoselenazole nucleus include naphtho [1,2-d] selenazole, Futho [2,1-d] selenazole and the like, as the thiazole nucleus, for example, thiazole nucleus, 4-methylthiazole nucleus, 4-
Phenylthiazole nucleus, 4,5-dimethylthiazole nucleus, 4,
Examples of the thiazoline nucleus such as 5-diphenylthiazole nucleus and the like include thiazoline nucleus and 4-methylthiazoline nucleus.

Regarding Z ₇₁ and Z ₇₂ , examples of the benzoxazole nucleus include a benzoxazole nucleus, a 5-chlorobenzoxazole nucleus, a 5-methylbenzoxazole nucleus, and a 5-methylbenzoxazole nucleus.
Bromobenzoxazole nucleus, 5-fluorobenzoxazole nucleus, 5-phenylbenzoxazole nucleus, 5-methoxybenzoxazole nucleus, 5-ethoxybenzoxazole nucleus, 5-trifluoromethylbenzoxazole nucleus, 5-
Hydroxybenzoxazole nucleus, 5-carboxybenzoxazole nucleus, 6-methylbenzoxazole nucleus, 6-chlorobenzoxazole nucleus, 6-methoxybenzoxazole nucleus, 6-hydroxybenzoxazole nucleus, 5,6-dimethylbenzoxazole nucleus, etc. As the naphthoxazole nucleus, for example, naphtho [2,1-d] oxazole nucleus,
Examples thereof include naphtho [1,2-d] oxazole nucleus, naphtho [2,3-d] oxazole nucleus, and 5-methoxynaphtho [1,2-d] oxazole nucleus.

Further regarding Z ₇₁ and Z ₇₂ , examples of the oxazole nucleus include an oxazole nucleus, a 4-methyloxazole nucleus, a 4-ethyloxazole nucleus, a 4-phenyloxazole nucleus, a 4-benzyloxazole nucleus, a 4-methoxyoxazole nucleus, A 4,5-dimethyloxazole nucleus, a 5-phenyloxazole nucleus, a 4-methoxyoxazole nucleus, or the like, and examples of the pyridine nucleus include a 2-pyridine nucleus, a 4-pyridine nucleus, and a 5-pyridine nucleus.
Methyl-2-pyridine nucleus, 3-methyl-4-pyridine nucleus, etc.
Examples of the quinoline nucleus include 2-quinoline nucleus, 4-quinoline nucleus, 3-methyl-2-quinoline nucleus, 5-ethyl-2-quinoline nucleus, 6-methyl-2-quinoline nucleus, 8-fluoro-4- Quinoline nucleus, 8-chloro-2-quinoline nucleus, 8-fluoro-2-quinoline nucleus, 6-methoxy-2-quinoline nucleus, 6-ethoxy-4-quinoline nucleus, 8-chloro-4-quinoline nucleus, 8- Methyl-4-quinoline nucleus,
8-methoxy-4-quinoline nucleus and the like can be mentioned.

Here, Z and Z ₉ are each a thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-phenylthiazoline, 4,5-dimethylthiazoline, 4,5-diphenylthiazoline, etc.), benzothiazoline nucleus ( For example, benzothiazoline, 4-chlorobenzothiazoline, 5-chlorobenzothiazoline, 6-chlorobenzothiazoline, 7-chlorobenzothiazoline, 5-nitrobenzothiazoline, 6-nitrobenzothiazoline, 4-methylbenzothiazoline, 5-
Methylbenzothiazoline, 6-methylbenzothiazoline,
5-bromobenzothiazoline, 6-bromobenzothiazoline, 5-iodobenzothiazoline, 5-methoxybenzothiazoline, 6-methoxybenzothiazoline, 5-ethoxybenzothiazoline, 5-propoxybenzothiazoline, 5-butoxybenzothiazoline, 5- Carboxybenzothiazoline, 5-ethoxycarbonylbenzothiazoline, 5-phenethylbenzothiazoline, 5-fluorobenzothiazoline,
5-chloro-6-methylbenzothiazoline, 5-trifluoromethylbenzothiazoline, 5,6-dimethylbenzothiazoline, 5-hydroxy-6-methylbenzothiazoline, tetrahydrobenzothiazoline, 4-phenylbenzothiazoline, 5-phenylbenzo Thiazoline, etc.), naphthothiazoline nucleus (for example, naphtho [2,1-d] thiazoline, naphtho [1,2-d] thiazoline, naphtho [2,3-d] thiazoline, 5-
Methoxynaphtho [1,2-d] thiazoline, 7-ethoxynaphtho [2,1-d] thiazoline, 8-methoxynaphtho [2,1-d] thiazoline, 5-methoxynaphtho [2,3-d] thiazoline, etc. ), A thiazolidine nucleus (eg, thiazolidine, 4-methylthiazolidine, 4-nitrothiazolidine, etc.), an oxazoline nucleus (eg, oxazoline, 4-methyloxazoline, 4-nitrooxazoline, 5-methyloxazoline, 4-
Phenyloxazoline, 4,5-diphenyloxazoline,
4-ethyloxazoline, etc.), benzoxazoline nucleus (benzoxazoline, 5-chlorobenzoxazoline,
5-methylbenzoxazoline, 5-bromobenzoxazoline, 5-fluorobenzoxazoline, 5-phenylbenzoxazoline, 5-methoxybenzoxazoline, 5-nitrobenzoxazoline, 5-trifluoromethylbenzoxazoline, 5-hydroxybenzoxazoline, 5-carboxybenzoxazoline, 6-methylbenzoxazoline, 6-chlorobenzoxazoline, 6-nitrobenzoxazoline, 6-methoxybenzoxazoline, 6-hydroxybenzoxazoline, 5,6-dimethylbenzoxazoline, 5-ethoxybenzoxazoline, etc. ), A naphthooxazoline nucleus (for example, naphtho [2,1-d] oxazoline, naphtho [1,2-d] oxazoline, naphtho [2,3-d] oxazoline, 5-nitronaphtho [2,1-d] oxazoline, etc. ), Oxazolidine nuclei (eg 4,4-dimethyl) Oxazolidine, etc.), selenazoline nucleus (eg, 4-methylselenazoline, 4-nitroselenazoline, 4-phenylselenazoline, etc.), selenazolidine nucleus (eg, selenazolidine, 4-methylselenazolidine, 4-phenylselenazolidine, etc.) , Benzoselenazoline nucleus (eg, benzoselenazoline, 5-chlorobenzoselenazoline, 5-nitrobenzoselenazoline, 5-methoxybenzoselenazoline, 5-hydroxybenzoselenazoline, 6-nitrobenzoselenazoline, 5-chloro -6-nitrobenzoselenazoline etc.),
Naphtho-selenazoline nucleus (eg naphtho [2,1-d] selenazoline, naphtho [1,2-d] selenazoline, etc.), 3,3-
Dialkylindoline nuclei (eg 3,3-dimethylindoline, 3,3-diethylindoline, 3,3-dimethyl-5-cyanoindoline, 3,3-dimethyl-6-nitroindoline, 3,3-
Dimethyl-5-nitroindoline, 3,3-dimethyl-5-methoxyindoline, 3,3-dimethyl-5-methylindoline, 3,3
-Dimethyl-5-chloroindoline, etc.), imidazoline nucleus (eg, 1-alkylimidazoline, 1-alkyl-4-phenylimidazoline, 1-arylimidazoline, etc.),
Benzimidazoline nucleus (eg 1-alkylbenzimidazoline, 1-alkyl-5-chlorobenzimidazoline, 1-
Alkyl-5,6-dichloro-benzimidazoline, 1-alkyl-5-methoxybenzimidazoline, 1-alkyl-5-cyanobenzimidazoline, 1-alkyl-5-fluorobenzimidazoline, 1-alkyl-5-trifluoromethyl Benzimidazoline, 1-allyl-5,6-dichlorobenzimidazoline, 1-allyl-5-chlorobenzimidazoline, 1-arylbenzimidazoline, 1-aryl-5-chlorobenzimidazoline, 1-aryl-5,6-dichloro Benzimidazoline, 1-aryl-5-methoxybenzimidazoline, 1-aryl-5-
Cyanobenzimidazoline), naphthoimidazoline nucleus (eg, 1-alkylnaphtho [1,2-d] imidazoline, 1-arylnaphtho [1,2-d] imidazoline),
The above-mentioned alkyls are especially those of 1 to 8 carbon atoms, eg
Unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and hydroxyalkyl groups (eg 2-
Hydroxyalkyl, 3-hydroxypropyl, etc.) are preferable. The aforementioned aryl group is phenyl, halogen (eg, chloro) -substituted phenyl, alkyl (eg, methyl).
Represents a substituted phenyl, an alkoxy (eg methoxy) substituted phenyl, and the like. Pyrrolidine nucleus (eg 2-pyrrolidine), dihydropyridine nucleus (eg 1,4-dihydropyridine, 5-methyl-1,2-dihydropyridine, 3-methyl-1,4-dihydropyridine etc.), dihydroquinoline nucleus (eg,
1,4-dihydroquinoline, 3-methyl-1,2-dihydroquinoline, 5-ethyl-1,2-dihydroquinoline, 6-methyl-1,2-dihydroquinoline, 6-nitro-1,2-dihydroquinoline , 8-
Fluoro-1,2-dihydroquinoline, 6-methoxy-1,2-dihydroquinoline, 6-hydroxy-1,2-dihydroquinoline, 8
-Chloro-1,2-dihydroquinoline, 6-ethoxy-1,4-dihydroquinoline, 6-nitro-1,4-dihydroquinoline, 8-chloro-1,4-dihydroquinoline, 8-fluoro-1,4 -Dihydroquinoline, 8-methyl-1,4-dihydroquinoline, 8-methoxy-1,4-dihydroquinoline, dihydroisoquinoline, 6-
Nitro-1,2-isoquinoline, 6-nitro-2,3-dihydroisoquinoline, etc.), represents a non-metal atomic group necessary to complete the tetrazoline nucleus, respectively.

Of these, Z and Z ₉ are preferably thiazoline nuclei, benzothiazoline nuclei, thiazolidine nuclei, benzoxazoline nuclei, naphthoxazoline nuclei, selenazoline nuclei, selenazolidine nuclei, benzoselenazoline nuclei, benzimidazoline nuclei, pyrrolidine nuclei, This is the case of a dihydropyridine nucleus and a tetrazoline nucleus. Z ₉ is particularly preferably a thiazoline nucleus, a thiazolidine nucleus, a selenazoline nucleus, a selenazolidine nucleus, a benzimidazoline nucleus, a pyrrolidine nucleus or a dihydropyridine nucleus. Further preferred as Z ₉ are a thiazoline nucleus, a thiazolidine nucleus, a benzimidazoline nucleus and a pyrrolidine nucleus.

R ₁ , R ₂ , R ₉₁ and R ₉₂ are each a hydrogen atom,
Unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to
8 alkyl groups such as methyl, ethyl, propyl,
Isopropyl, butyl, hexyl, dodecyl octadecyl etc.), substituted alkyl group [eg aralkyl group (eg benzyl, β-phenylethyl etc.), hydroxyalkyl group (eg 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxyethoxy) Ethyl, etc.), carboxyalkyl group (eg, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, etc.), alkyl group substituted with a sulfo group (sulfo group is an alkoxy group or an aryl group) And may be bound to an alkyl group, for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-
Sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, p-sulfophenethyl and the like), sulfate alkyl group (eg, 3-sulfatepropyl, 4-sulfate) Butyl, etc.), mercapto group, vinyl group-substituted alkyl group (eg, allyl group), acyloxyalkyl group (eg,
2-acetoxyethyl group, 3-acetoxypropyl group, etc., alkoxyalkyl group (eg, 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxycarbonylalkyl group (eg, 2-methoxycarbonylethyl group, 3- Methoxycarbonylpropyl group, 4-ethoxycarbonylbutyl group, etc.), Cyanoalkyl group (eg, 2-
Cyanoethyl group), carbamoylalkyl group (eg, 2-carbamoylethyl group), aryloxyalkyl group (eg, 2-phenoquinethyl group, 3-phenoxypropyl group), aryloxyalkyl group (eg,
2-phenoxyethyl group, 3-phenoxypropyl group etc.), mercaptoalkyl group (eg 2-mercaptoethyl group, 3-mercaptopropyl group etc.), alkylthioalkyl group (eg 2-methylthioethyl group etc.), or aryl Represents a group (eg, phenyl group, tolyl group, naphthyl group, methoxyphenyl group, chlorophenyl group, etc.). R ₂ and R ₉₂ are preferably a hydrogen atom or an allyl group.

Q and Q ₉ are each a rhodanine nucleus, a 2-thiooxazoline-2,4-dione nucleus, a 2-thioselenazoline-2,4-dione nucleus, a barbituric acid nucleus or a thiobarbituric acid nucleus [eg 1-alkyl. Groups (eg 1-methyl, 1-ethyl, 1-propyl, 1-hebutyl, etc.), 1,3-dialkyl groups (eg 1,
3-dimethyl, 1,3-diethyl, 1,3-dipropyl, 1,3-diisopropyl, 1,3-dicyclehexyl, 1,3-di (β-methoxyethyl), etc.), 1,3-diaryl group (For example, 1,3-diphenyl, 1,3-di (p-chlorophenyl), 1,3-di (p-ethoxycarbonylphenyl), etc.), 1-sulfoalkyl group (for example, 1- (2-sulfoethyl), 1- (3-sulfopropyl),
1- (4-sulfohebutyl) etc.), 1,3-disulfoalkyl group (for example, 1,3-di (2-sulfoethyl), 1,3-di (3-sulfopropyl), 1,3-di- ( 4-sulfocyclohexyl), 1,3-
Barbitur nucleus or thiol containing di- (sulfoaryl group (eg 1,3-di- (4-sulfophenyl) etc.) or 1-sulfoaryl group (eg 1- (4-sulfophenyl) etc.) Barbituric acid nucleus], or a thiohydantoin nucleus (the substituent at the 1-position is synonymous with the 3-position (R ₂ , R ₉₂ ) but both may be the same or different) Represents a group of metal atoms.

The heterocyclic ring formed by Q and Q ₉ is preferably a rhodanine nucleus or a thiohydantoin nucleus, more preferably a rhodanin nucleus.

Y ₉₁ and Y ₉₂ are hydrogen atoms, alkyl groups (eg methyl group, ethyl group, propyl group, benzyl group), aryl groups (eg phenyl group, o-carboxyphenyl group, p-carboxyphenyl group, etc.) ) Represents. m
Represents 0, 1, or 2. p represents 0 or 1.

The compounds represented by the general formulas [1] to [3] of the present invention are 10 ^-5 to 10 per mol of silver in a silver halide emulsion.
^It is suitable to add ^-1 mol (preferably 10 ^-4 to 10 ^-2 mol) .When adding these, it is possible to dissolve them in alcohols such as methanol and ethanol, ethers, ketones, ethylene glycol, diethylene glycols. Then it can be added to the emulsion. Generally, the sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of the sensitizing dyes is often used particularly for the purpose of supersensitization.

Specific examples of the compound of the general formula [1] used in the present invention include the following.

[0027]

[Chemical 5]

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

The following are specific examples of the compound of the general formula [2] used in the present invention.

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

The following are specific examples of the compound of the general formula [3] used in the present invention.

[0047]

[Chemical formula 23]

[0048]

[Chemical formula 24]

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28]

[0053]

[Chemical 29]

[0054]

[Chemical 30]

[0055]

[Chemical 31]

[0056]

[Chemical 32]

The silver halide emulsion used in the present invention (hereinafter referred to as a silver halide emulsion or simply an emulsion) includes, for example, silver bromide, silver iodobromide, silver iodochloride, chloroodor. Although any of those used for ordinary silver halide emulsions such as silver halide and silver chloride can be used, silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride are preferable. Or it is silver chloride.

[(Standard deviation of particle size)] / (average value of particle size)
Monodisperse particles represented by × 100 and having a coefficient of variation of 15% or less are preferable.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention.

For example, in the silver halide photographic emulsion and backing layer used in the present invention, various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents,
A development inhibitor, an ultraviolet absorber, an anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion of the present invention and the backing layer.

These additives are described in more detail in Research Disclosure Vol. 176 Item / 7643 (December 1978) and Vol. 187 Item / 8716 (November 1979). It is summarized below.

Additive type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent Page 27 As above As a support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, promhydroquinone, 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-virazolidone, 1-phenyl-5-methyl -
3-pyrazolidone), aminophenols (eg
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-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-
Methylphenyl) -3-aminopyrazoline etc.)
Although they can be used alone or in combination, it is preferable to use them in a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes. The developing agent is usually 0.
It is preferably used in an amount of 01 to 1.4 mol / l.

In the present invention, examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably 0.25 mol / l or more. It is particularly preferably 0.4 mol / l or more.

In the developer, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.), a silver sludge inhibitor (Japanese Patent Publication No. 62-4702, JP-A-3-51844, and JP-A-4-51844).
26838, JP-A-4-362942, JP-A-1-31903
1) pH buffering agents (eg carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.), solubilizing agents (eg polyethylene glycols,
Their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoamers, antifoggants (eg potassium bromide) , Silver halides such as sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole,
Benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc.), development accelerators (eg US Pat. No. 2,304,
No. 025, Japanese Patent Publication No. 47-45541, etc.), a hardener (eg, glutaraldehyde or its bisulfite adduct), or an antifoaming agent can be added. The pH of the developer is preferably adjusted to 9.5-12.0.

The compound of the present invention is used in an activator processing solution containing a developing agent in a light-sensitive material, for example, an emulsion layer, and processing the light-sensitive material in an alkaline aqueous solution to perform development as a special form of development processing. Good. Such development processing is often used as one of the rapid processing methods for the light-sensitive material in combination with the silver salt stabilization processing with thiocyanate, and can be applied to such processing solutions. . In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing solution, those having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer and others, and the pH is usually 3.8 to 5.8. As a fixing agent, sodium thiosulfate, potassium thiosulfate,
Use of thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, as well as organic sulfur compounds capable of forming soluble stable silver complex salts, which are known as fixing agents. You can

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

If desired, the fixer may include preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid), pH adjusters (eg, sulfuric acid), chelating agents having a water softening ability, etc. Can be included.

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

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

The black and white silver halide photographic light-sensitive material according to the present invention is preferably processed using an automatic processor.
At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The development replenishment amount is 250 ml or less per 1 m ² in order to reduce the amount of waste liquid. It is preferably 75 ml or more and 200 ml or less per 1 m ² . Particularly preferably not more than 1 m ² per 75ml or 150 ml, 1 m ² per 7
If the developer replenishment amount is less than 5 ml, satisfactory photographic performance cannot be obtained due to desensitization and softening.

According to the present invention, in order to shorten the developing time, the total processing time (Dry to Dry) from when the film front end is inserted into the automatic developing machine to when it comes out of the drying zone is set when the processing is performed by using the automatic developing machine. It is preferably 20 to 60 seconds. The total processing time referred to here includes all process times required for processing a black and white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilization processing and drying necessary for processing. The time including all process times, that is, Dr
It's y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

A compound represented by the following general formula [5] is preferably added to the developing solution which can be used in the present invention.

[0075]

[Chemical 33]

In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom, -SM
₁ group, a hydroxy group, a lower alkoxy group-COOM ₂ group, an amino group, -SO ₃ M ₃ group or a lower alkyl group, R ₁ ,
At least one of R ₂ and R ₃ represents a —SM ₁ group. M ₁ ,
M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different.

In the above general formula [5], R ₁ , R ₂ ,
The lower alkyl group and the lower alkoxy group represented by R ₃ are each a group having 1 to 5 carbon atoms, which may further have a substituent, preferably 1 to 5 carbon atoms.
The amino group represented by R ₁ , R ₂ and R ₃ is a group having 3 groups, represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group.

In the above general formula [5], the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

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

[0080]

[Chemical 34]

[0081]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 (Preparation of silver halide photographic emulsion A) A silver chloroiodobromide emulsion (70 mol% of silver chloride and 0.2 mol% of silver iodide per 1 mol of silver) was prepared by the simultaneous mixing method. K ₃ RhCl ₆ was added to silver 1
8.1 × 10 ⁻⁷ mol was added per mol. The emulsion obtained is
Cubic monodisperse particles with an average particle size of 0.20 μm (coefficient of variation 9
%). Modified gelatin (JP-A-2-28
No. 0139 G-8) was added, washed with water and desalted. The EAg at 50 ° C. after desalting was 190 mV.

[0083]

[Chemical 35]

Subsequently, the temperature of the emulsion was adjusted to 60.degree.
The H was adjusted to 5.58 and the EAg was adjusted to 123 mV.

HAuCl ₄ was added in an amount of 2.2 × 10 ^-5 mol per mol of silver, and after stirring for 2 minutes, S ₈ was added in an amount of 2.9 × 10 ^-6 mol per mol of silver, and the mixture was further stirred for 78 minutes for chemical sensitization. . Upon completion of the chemical sensitization, the following compounds were added and then the temperature was lowered to 40 ° C. to complete the chemical sensitization.

[0086]

[Chemical 36]

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm, the backing surface side of which is described in JP-A-3-92175 In addition, the silver halide emulsion layer of the following formulation (1) had a gelatin content of 2.6 g / m ² and a silver content of 3.
It is coated so that it will be 3 g / m ^2, and the following formulation (2)
The emulsion protective layer of 1 is coated so that the amount of gelatin is 1.0 g / m ^2, and the following formulation (3) is applied on the other undercoat layer on the opposite side.
A backing layer is coated according to the procedure described above so that the amount of gelatin is 2.7 g / m ^2, and a backing protective layer having the following formulation (4) is further coated thereon so that the amount of gelatin is 1 g / m ^2. No.
1-18 were obtained.

Formulation (1) [Silver halide emulsion layer composition] Gelatin 2.6 g / m ² Silver halide emulsion A Silver amount 3.3 g / m ² Sensitizing dye (shown in Table 1)
7.8 mg / m ²

[0089]

[Chemical 37]

[0090]

[Chemical 38]

[0091]

[Chemical Formula 39]

Gelatin 2.
7 g / ^{m 2} Surfactant: Saponin ^{133mg / m 2: S-1} 6mg / m 2 Colloidal silica 100 mg / m ² Compound E
100 mg / m ² prescription (4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Monodisperse polymethylmethaacrylate with average particle size 5.0 μm 50 mg / m ² Surfactant: S-3 10 mg / m ² Hard Membrane agent: Glyoxal 5mg / m ²

[0093]

[Chemical 40]

The obtained sample was exposed to a high illuminance of 10 ^-6 seconds through a 488 nm interference filter as a substitute light source of an argon laser with a step wedge in close contact, and then a developing solution and a fixing solution having the compositions shown below were added. Processing was carried out under the following conditions with an automatic processor GR-26SR for rapid processing manufactured by Konica Corporation.

Developer Formulation Sodium Sulfite 55g Potassium Carbonate 40g Hydroquinone 24g 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (Dimeson S) 0.9g Potassium Bromide 5g 5-Methyl-benzotriazole 0.13g 1- Phenyl-5-mercaptotetrazole 0.02g Boric acid 2.2g Diethylene glycol 40g Compound 5-1 60mg Add water and potassium hydroxide to finish to 1 liter pH 1
It was set to 0.5.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure water (Ion-exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (AI ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g When the fixer is used, the above composition A is added to 500 ml of water. , Composition B were melted in this order and finished to 1 l for use. The pH of this fixer was adjusted to 4.8 with acetic acid.

[0097] The concentration of the obtained sample was measured with an optical densitometer, Konica PDA-65,
Sensitivity is the reciprocal of the exposure amount that gives a fog density of +3.5, and is shown as relative sensitivity with sample No. 1 sensitivity as 100.

It was determined from the slope of the characteristic curve in 1 to 3.5.

The results are shown in Table 1.

[0100]

[Table 1]

As is clear from Table 1, the sample containing the compound of the present invention has high sensitivity, high maximum concentration, and high gamma.

Example 2 Example 1 A sample was prepared in the same manner as in Example 1 except that the sensitizing dyes shown in Table 2 were used instead of the sensitizing dyes shown in Table 1, and the following evaluations were carried out.

The addition amount of the sensitizing dye is 2.2 mg / in the dye of the present invention.
m ² and comparative dye D were 7.8 mg / m ² .

[Evaluation of halftone dot quality (DQ)] A C-690-DX plate-making camera (Dainippon Screen Co., Ltd.) was used to measure the sample through a commercially available contact screen (gray negative 150 lines).
Manufactured stepwise exposure, and then the development processing described in Example 1 was performed to obtain halftone dot areas of 10%, 50% and 95% respectively.
Five-level evaluation was performed by visual observation with a 100-fold magnifying glass.

Rank 1 is the lowest in quality, and rank 5 is the best. Rank 3 is the limit for practical use.

[Exposure and processing conditions] The obtained sample was exposed to xenon light for 3 seconds with a step wedge adhered thereto, and then a developing solution and a fixing solution of the above composition were added to Konica Corporation.
Processing was carried out under the above conditions using a rapid processing automatic processor GR-26SR manufactured by the same company. The sensitivity and gamma were evaluated in the same manner as in Example 1.

The results are shown in Table 2.

[0108]

[Table 2]

From the results shown in Table 2, it can be seen that the sample using the sensitizing dye of the present invention has high sensitivity, high gamma, and good dot quality.

[0110]

According to the present invention, there is provided a silver halide photographic light-sensitive material which has high sensitivity and high contrast even when processed with a developing solution having a relatively low pH (11.0 or less), and which has a good density of halftone dots. We were able to.

Claims (3)

[Claims] 1. A support having at least one silver halide emulsion layer and / or another hydrophilic colloid layer,
In a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator in the silver halide emulsion layer and / or the hydrophilic colloid layer, the silver halide emulsion layer and / or
Alternatively, a silver halide photographic light-sensitive material comprising a hydrophilic colloid layer containing a compound represented by the following general formula [1]. [Chemical 1] [In the formula, Z is a thiazoline nucleus, thiazolidine nucleus, selenazoline nucleus, selenazolidine nucleus, pyrrolidine nucleus, dihydropyridine nucleus, oxazoline nucleus, oxazolidine nucleus, imidazoline nucleus, indoline nucleus, tetrazoline nucleus, benzothiazoline nucleus, benzoselenazoline nucleus, benzimidazoline nucleus. It represents a group of non-metal atoms necessary for completing a nucleus, a benzoxazoline nucleus, a naphthothiazoline nucleus, a naphthoselenazoline nucleus, a naphthoxazoline nucleus, a naphthimidazoline nucleus or a dihydroquinoline nucleus. Q represents an atomic group necessary for completing a rhodamine nucleus, a 2-thiooxazoline-2,4-dione nucleus, a 2-thiohydantoin nucleus, a barbituric acid nucleus or a 2-thiobarbituric acid nucleus. R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. p represents 0 or 1. ] 2. A support having at least one silver halide emulsion layer and / or another hydrophilic colloid layer,
In a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator in the silver halide emulsion layer and / or the hydrophilic colloid layer, the silver halide emulsion layer and / or
Alternatively, a silver halide photographic light-sensitive material characterized by containing a compound represented by the following general formula [2] in the hydrophilic colloid layer. [Chemical 2] [In the formula, Z ₇₁ and Z ₇₂ are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, thiazole nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus, and selenazoline, respectively. It represents a group of non-metal atoms necessary to complete a nucleus, a pyridine nucleus, or a quinoline nucleus. R ₇₁ and R ₇₂ represent a substituted or unsubstituted alkyl group. X ₇ ^- represents an acid anion, n represents 0 or 1. ] 3. A support having at least one silver halide emulsion layer and / or another hydrophilic colloid layer,
In a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator in the silver halide emulsion layer and / or the hydrophilic colloid layer, the silver halide emulsion layer and / or
Alternatively, a silver halide photographic light-sensitive material characterized in that the hydrophilic colloid layer contains a compound represented by the following general formula [3]. [Chemical 3] [In the formula, Z ₉ is a thiazoline nucleus, thiazolidine nucleus, selenazoline nucleus, selenazolidine nucleus, pyrrolidine nucleus, dihydropyridine nucleus, oxazoline nucleus, oxazolidine nucleus, imidazoline nucleus, indoline nucleus, tetrazoline nucleus, benzothiazoline nucleus, benzoselenazoline nucleus, benz It represents a group of emergency metal atoms necessary to complete an imidazoline nucleus, a benzoxazoline nucleus, a naphthothiazoline nucleus, a naphthoselenazoline nucleus, a naphthoxazoline nucleus, a naphthimidazoline nucleus or a dihydroquinoline nucleus. Q ₉ is a rhodanine nucleus, 2-thiooxazoline-2,4-dione nucleus, 2-thioselenazoline-2,
Represents a group of non-metal atoms required to complete a 4-dione nucleus, a barbituric acid nucleus or a 2-thiobarbituric acid nucleus. R ₉₁ and R ₉₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Y ₉₁ and Y ₉₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. p represents 0 or 1. However, the following general formula [4] is excluded] [In the formula, R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ , R ₁₀₅ represent a substituted or unsubstituted alkyl group or aryl group. ]