JP3371648B2 - Developing method of silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide black and white photographic light-sensitive material for forming a silver image as a final image .
The present invention relates to a development processing method , and more specifically, it can be handled in an environment substantially called a bright room and can form a negative tone silver image with high contrast, which is suitable for the field of photoengraving The present invention relates to a method for developing a silver halide black and white photographic light-sensitive material.

[0002]

2. Description of the Related Art Among photoengraving processes in the field of print reproduction, particularly in the work processes of collecting and returning plates, the work efficiency and work environment are improved by working in a brighter environment. That is, there is provided a silver halide photographic light-sensitive material for plate making that can be handled in an environment that can be called a bright room. A method of making a light-sensitive material that can be handled in a bright room by reducing its sensitivity to visible light is to use a silver halide emulsion mainly composed of silver chloride with an inorganic material such as rhodium salt, iridium salt, pinacryptol yellow, and phenosafranine. It is well known to use an emulsion to which an organic desensitizer is added. 0.05 to which chemical sensitization is not applied
A method of using a rhodium salt and / or an organic desensitizer in a 0.5 μm fine grain silver chloride or fine grain silver chlorobromide emulsion is preferably used. Furthermore, in combination with these emulsions, for the purpose of sensitivity adjustment and safelight safety,
A method of incorporating a yellow dye or an ultraviolet absorbing dye into the photosensitive material is used.

On the other hand, the light-sensitive material used in the plate-collecting and reversing process has the following features:
There is a demand for what has a so-called ultra-high contrast photographic property, which has a high blackening density in which image areas and non-image areas are clearly distinguished. In particular, the halftone image and the line image original as the return original are overlapped and exposed (so-called character image formation is performed).
In this case, there is a demand for a light-sensitive material having good line drawing reproduction performance (extracted character quality).

As a method for imparting ultra-high contrast photographic characteristics to a light-sensitive material, a method of incorporating a vitrazine derivative or a tetrazolium compound into the light-sensitive material is known, and the above-mentioned inorganic and organic desensitizers and yellow. When a method of incorporating a dye or an ultraviolet-absorbing dye into the light-sensitive material is combined, problems may occur such that the contrast enhancement effect of the hydrazine derivative or tetrazolium compound is obstructed and good line drawing reproduction performance is lost. It was

As an image system capable of obtaining ultrahigh contrast photographic characteristics in a silver halide black and white photographic light-sensitive material for return,
JP-A-60-140338, JP-A-61-238049
No. 63-183438, No. 63-296034.
No. 61-198147, No. 61-198148.
No. 61-240235. However, the pH of the developer used in these inventions is 11 or more. A developer with a pH of 11 or more is easily oxidized by air and is unstable and cannot withstand long-term storage. Therefore, a silver halide photographic light-sensitive material containing a hydrazine derivative is developed with a developer having a lower pH to obtain a high contrast image. Is required.

However, when the pH of the developing solution is low, the effect of the hydrazine-based nucleating agent for reducing the contrast decreases, and it is difficult to obtain a contrast-rich image. Further, when the replenishment amount of the developing solution is reduced, the tendency becomes even stronger and it is difficult to obtain a high-contrast image, and there is a problem that the practical density decreases during the processing and running, and improvement has been strongly desired.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a reversal silver halide photographic light-sensitive material which can be handled under bright safelight (substantially in a bright room) and has a high contrast photographic property . It is to provide a development processing method .
A second object of the present invention is a method for developing a silver halide photographic light-sensitive material for return, which has a high practical skill Dmax, does not fluctuate in practical skill Dmax even when processed with a fatigue solution, and is excellent in the image quality of blank characters. /> Is to be provided.

[0008]

These objects of the present invention are, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer containing Ir, Ru. Halogenation containing a heavy metal ion selected from Rh, Rh, Re, and Cr in an amount of at least 1 × 10 ^-6 mol per mol of silver halide and chemically sensitized with a gold compound and a sulfur compound and having a silver chloride content of 95 mol% or more. It comprises silver particles, at least one layer of the emulsion layer and / or other hydrophilic colloid layers in the following general formula (1)
There are few hydrazine derivatives in which R ₂ is a hydrogen atom.
And R ₂ is an alkyl group in the following general formula (1).
Group, aryl group, unsaturated heterocyclic group, alkoxy group,
An aryloxy group, an amino group or a hydrazino group
The silver halide photographic material containing at least one and nucleation accelerator hydrazine derivatives, achieved by the developing method for processing a silver halide photographic light-sensitive material characterized that you treated with pH11.0 following developer Was done . General formula (1)

[0009]

[Chemical 3]

In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. And G ₁ is a —CO— group,
-SO ₂ - group, -SO- group,

[0011]

[Chemical 4]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (1), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent.

Generally, a silver halide emulsion for bright room use has a low sensitivity because it is heavily doped with heavy metal ions from the viewpoint of safelight safety. Therefore, the nucleation developability of the hydrazine derivative is low and it is difficult to obtain a hard image. Also,
There is a problem that the tendency is further enhanced when processing is performed with a developer having a low pH. In the present invention, an emulsion heavily doped with heavy metal ions is subjected to chemical sensitization such as gold sulfur sensitization or gold sulfur selenium sensitization, and in the general formula (1) , R ₂ is a hydrogen atom.
At least one hydrazine derivative having the general formula
In (1), R ₂ is an alkyl group, an aryl group, or unsaturated
Heterocyclic group, alkoxy group, aryloxy group, amino
Of hydrazine derivatives that are hydrazine or hydrazino groups
Halogen containing 1 type together with a nucleation accelerator
It has been found that by using a silver halide photographic light-sensitive material, ultra-high contrast photographic characteristics can be obtained even with a developing solution having a low pH, and the practical Dmax does not fluctuate even during processing running.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The silver halide emulsion of the present invention comprises Ir, Ru, Rh, R
At least one heavy metal ion selected from e and Cr is contained. Preferred as these heavy metal ions are
It is a metal coordination complex and is a hexacoordination complex represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (In the formula, M is a heavy metal ion selected from Ir, Ru, Rh, Re, and Cr. L is a bridging ligand. Y is oxygen or sulfur. Yes, m = 0, 1, 2, n = 0,-
It is 1, -2, and -3. ) Preferred examples of L are halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyan. Nate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands. Specific examples of the metal coordination complex are shown below. 1. [Rh (H ₂ O) Cl ₅ ] ^-2 2. [RuCl ₆ ] ^-3 3. [Ru (NO) Cl ₅ ] ^-2 4. [RhCl ₆ ] ^-3 5. [Ru (H ₂ 0) Cl ₅ ] ^-2 6. [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 7. [Re (NO) Cl ₅ ] ^-2 8. [Ir (NO) Cl ₅ ] ^-2 9. [Ir (H ₂ 0) Cl ₅ ] ^-2 10. [Re (H ₂ 0) Cl _5] ^-2 11. [RhBr _6] ^-3 12. [ReCl _6] ^-3 13. [IrCl _6] ^-3 14. _{[Re (NS) Cl 4 (SeCN} ) ] ^{- 2} 15. [Cr (CN) ₆ ] ^-3

The metal complex can be added to the silver halide during grain preparation. The content of the heavy metal in the silver halide grains of the present invention is 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide. Preferably 10 ^{−6 to} 3 × 10 ⁻⁴ mol and further 1 × 10
^-6 mol to 3 × 10 ^-5 mol. Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grain is not particularly limited, but it is preferable that the heavy metal is more present outside the grain.

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

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

In the present invention, the grain formation of the silver halide emulsion is preferably carried out under acidic conditions. This is effective in suppressing the fog due to the chemical sensitization by the gold-sulfur sensitizer performed thereafter. The acidic condition is pH
4.0 or less, preferably pH 3.0 to pH 1.5
Is.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is chemically sensitized after grain formation, that is, gold sulfur sensitization, with a gold sensitizer and a sulfur sensitizer. As the above gold sensitizer, + even if the oxidation number of gold is +1
A trivalent compound may be used, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide.
Known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US Patent No. 1,5
74,944, 2,410,689, 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The amount of the sulfur sensitizer added varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but 1 × 10 ⁻⁷ mol or more per mol of silver halide, 5x
It is preferably 10 ^-4 mol or less. Chemical sensitization with these sensitizers is performed by adding the sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher, for a certain period of time.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is more preferably subjected to gold sulfur selenium sensitization in combination with a selenium sensitizer. As the selenium sensitizer preferably used in the present invention, the selenium compounds disclosed in the conventionally known patents can be used. That is, it is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, Japanese Patent Publication No. 44-
No. 15748, Japanese Examined Patent Publication No. 43-13489, JP-A-4-
No. 25832, JP-A-4-109240, and Japanese Patent Application No. 3-
It is preferable to use the compounds described in No. 92929 and the like. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropions, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, etc. can give. The preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and play no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention are JP-B-46-4553,
JP-B-52-34492 and JP-B-52-3449
The compound described in No. 1 is used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (A) and (B) are preferable. General formula (A)

[0022]

[Chemical 5]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represent an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg vinyl group, propenyl group), aralkyl group (eg benzyl group, phenethyl group), aryl group (eg phenyl group, penta) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR
₁ (R _2), - represent OR ₃ or -SR _4. R ₁ ,
R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group include the same examples as Z ₁ . However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-
A trifluoromethylbenzoyl group). In formula (A), preferably Z ₁ represents an alkyl group, an aryl group or —NR ₁ (R ₁ ), and Z ₂ represents —NR.
Represents ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (A), more preferably N, N-dialkylselenourea, N, N, N′-trialkyl-N′-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N -Alkyl-N-aryl-arylselenoamide. General formula (B)

[0024]

[Chemical 6]

In the formula, Z ₃ , Z ₄ and Z _{5, which} may be the same or different, each represents an aliphatic group, an aromatic group, a heterocyclic group,
-OR ₇ , -NR ₈ (R ₉ ), -SR ₁₀ , -SeR ₁₁ ,
X represents a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom.
In the general formula (B), Z ₃ , Z ₄ , Z ₅ , R ₇ ,
The aliphatic group represented by R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n-propyl group, Isopropyl group, t-butyl group,
n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group,
Allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group, phenethyl group). In the general formula (B), Z ₃ , Z ₄ , Z
_The aromatic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (for example, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-sulfo group). Phenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (B),
Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁
The heterocyclic group represented by is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom (for example, a pyridyl group, a thienyl group, a furyl group, a thiazolyl group. , An imidazolyl group, and a benzimidazolyl group). In the general formula (B),
The cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In the general formula (B), Z ₃ , Z ₄ or Z ₅ is preferably an aliphatic group, an aromatic group or-
Represents OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. In formula (B), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (A) and (B) are the compound examples I-1 to I-20 and II-21 to II- described in Japanese Patent Application No. 6-250156.
43 can be mentioned.

Specific examples of selenium sensitizers which are particularly preferable for exhibiting the effects of the present invention are shown below, but the present invention is not limited thereto.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

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

In addition to these sensitizers, a noble metal such as platinum or palladium, a first tin salt, an amine, a reduction sensitizer such as formamidinesulfinic acid or a silane compound may be used in combination. The silver halide grains of the present invention are preferably added with a thiosulfonic acid compound represented by the following general formulas (C), (D) and (E) in the steps of grain formation and / or gold sulfur sensitization. This makes it possible to obtain an emulsion with further reduced fog. (C) in _{R-SO 2 S-M (} D) R-SO 2 S-R 1 (E) R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is the same They may be different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, m is 0 or 1
Is. The compounds of the general formulas (C) to (E) are represented by (C)
To (E) may be a polymer containing a divalent group derived from the structure represented by (E) as a repeating unit. Specific examples of the general formulas (C) to (E) are shown below.

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

The hydrazine derivative used in the present invention is
It is represented by the following general formula (1). General formula (1)

[0042]

[Chemical 19]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. And G ₁ is a —CO— group,
-SO ₂ - group, -SO- group,

[0044]

[Chemical 20]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (1), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. In the general formula (1),
The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamido group,
Sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having hydrazide structure, group having quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group , Carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, phosphoramide group, diacylamino group, imide group, group having acylurea structure, selenium atom or Examples thereof include a group containing a tellurium atom, a group having a tertiary sulfonium structure or a group having a quaternary sulfonium structure, and a preferable substituent is a linear, branched or cyclic alkyl group (preferably having a carbon number of 1).
~ 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably Amino group substituted with alkyl group having 1 to 20 carbon atoms, acylamino group (preferably having 2 carbon atoms)
To 30), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Stuff).

In the general formula (1), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable. Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
Hydrogen atom, alkyl group (for example, methyl group, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.),
Aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc. ) And so on. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferable.
As G in the general formula (1), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. Also, R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group Can be mentioned)). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (1) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent ...
., May be multiply substituted, and preferred examples are also those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (1) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R _{2 in} the general formula (1) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in U.S. Pat. Nos. 4,385,108 and 4,459,34.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of a silver halide grain, a group having a quaternary ammonium structure or an alkylthio group. A phenyl group having a group, G
Is a —CO— group and R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

In the present invention, at least two kinds of the above hydrazine derivatives are included. R ₂ of at least one of the hydrazine derivatives is a hydrogen atom. In the other hydrazine derivative, R ₂ is an alkyl group, an aryl group, or an unsaturated heterocycle.
Group, alkoxy group, aryloxy group, amino group or
A hydrazine derivative represented by a hydrazino group and having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group is particularly preferably used.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means that an atom 2 to 5 selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is present between the nitrogen atom close to the anionic group of hydrazine and the anionic group.
It means that there is an intervening bond chain formed by individuals. More preferably as a neighborhood, there is an intervening bond chain formed of 2 to 5 atoms selected from at least one of carbon and nitrogen atoms, and even more preferably a bond chain formed of 2 to 3 carbon atoms. This is when intervening. The nonionic group forming an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and contains at least an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following general formulas (2) to (4). General formula (2)

[0055]

[Chemical 21]

(Wherein R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine). Represents a nonionic group forming an intramolecular hydrogen bond.) General formula (3)

[0057]

[Chemical formula 22]

(In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (4)

[0059]

[Chemical formula 23]

(In the formula, X ³ represents a group capable of substituting for a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (2) to (4) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl and 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, and examples thereof include phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl and p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amido group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

[0064] alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Is a linear, branched or cyclic alkoxy group, and is, for example, methoxy, isopropoxy or benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group or an alkynyl group. n ³ =
When 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group of R ³ has a Hammett σ _m value of 0.2 or more, preferably 0.3.
Examples of the above include halogen atoms (fluorine, chlorine, bromine), cyano groups, sulfonyl groups (methanesulfonyl, benzenesulfonyl), sulfinyl groups (methanesulfinyl), acyl groups (acetyl, benzoyl), oxycarbonyl groups (methoxycarbonyl). ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group and their -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-butene-1,4-yl, 2
-Butyn-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

Examples of the electron-withdrawing group possessed by L ¹ include R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). The nonionic group is a group having at least one of an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. As Y ¹ to Y ³ , an anionic group is preferable, and a carboxylic acid and its salt are more preferable.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable groups include those mentioned as the substituents of R ^{1 in the} general formula (2). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler, or may have an adsorption promoting group to silver halide. The diffusion resistant group has 8 to 30 carbon atoms, preferably 12 to 25 carbon atoms. The adsorption promoting group for silver halide is preferably a thioamide (eg thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
Is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorbing group is protected and the protecting group is removed during the development processing to enhance the adsorptivity to silver halide.

In the general formulas (2) to (4), radicals from which hydrogen atoms of two compounds are removed may combine with each other to form a bis type. In the general formulas (2) to (4), the general formulas (2) and (3) are preferable, and the general formula (2) is more preferable. Furthermore, in the general formulas (2) to (4), the following general formulas (5) to (7) are more preferable, and the general formula (5) is most preferable. General formula (5)

[0072]

[Chemical formula 24]

(Wherein R ⁴ , X ⁴ and m ⁴ have the same meanings as R ³ , X ³ and m ^{3 in the} general formula (4), respectively, and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ^{1 in} the general formula (2). ) General formula (6)

[0074]

[Chemical 25]

(In the formula, R ⁵ , X ⁵ and m ⁵ have the same meanings as R ³ , X ³ and m ^{3 in the} general formula (4), respectively, and L ⁵ , Y ^{5 and}
Is synonymous with L ² and Y ^{2 in} the general formula (3). ) General formula (7)

[0076]

[Chemical formula 26]

(Wherein R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y is R ³ , R ³ , X ³ , m ³ , n ³ or Y in the general formula (4).
Synonymous with ³ . )

Specific examples of the hydrazine derivative used in the present invention are shown below, but the present invention is not limited thereto.

[0079]

[Chemical 27]

[0080]

[Chemical 28]

[0081]

[Chemical 29]

[0082]

[Chemical 30]

[0083]

[Chemical 31]

[0084]

[Chemical 32]

[0085]

[Chemical 33]

[0086]

[Chemical 34]

[0087]

[Chemical 35]

[0088]

[Chemical 36]

[0089]

[Chemical 37]

[0090]

[Chemical 38]

[0091]

[Chemical Formula 39]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442.
No. 2-220042, No. 2-221953, No. 2-221954, No. 2-285342, No. 2-2.
85343, 2-289843, 2-3027.
No. 50, No. 2-304550, No. 3-37642,
No. 3-54549, No. 3-125134, No. 3-1
No. 84039, No. 3-240036, No. 3-2400.
No. 37, No. 3-259240, No. 3-280038.
No. 3, No. 3-228536, No. 4-51143, No. 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
The thing described in Japanese Patent Application No. 5-94925 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, and particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method. Further, as described in JP-A-2-948, it can be used by being contained in fine polymer particles.

The silver halide photographic light-sensitive material of the present invention preferably contains a nucleation accelerator in at least one of the emulsion layer and other hydrophilic colloid layers.

Nucleation accelerators preferably used in the present invention are compounds represented by the following general formulas (8), (9), (10) and (11).

[0097]

[Chemical 40]

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group bonded to the P atom by its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents May be linked to L.

[0099]

[Chemical 41]

In the formula, A represents an organic group for completing the heterocycle. B and D each represent a divalent group.
R ₁ and R ₂ each represent an alkyl group or an aryl group,
R ₃ and R ₄ represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt.

Details and compounds of the compounds represented by the general formulas (8) to (11) can be found in the description in Japanese Patent Application No. 6-250136 and the compound examples A201 to A262 therein. Many of the compounds represented by the general formula (8) are known and are commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method.

The compounds represented by the general formula (9), the general formula (10) and the general formula (11) can be synthesized by a generally well-known method (for example, Quart. Rev., 16, 163 (19).
62))).

General formula (8), general formula (9), general formula (1
0), the addition amount of the compound of the general formula (11) is not particularly limited, but it is preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol per mol of silver halide, particularly 2 ×.
The preferable addition amount is in the range of 10 ⁻⁵ to 1 × 10 ⁻² mol. The nucleation accelerator used particularly preferably in the present invention is a compound represented by the general formula (10).

When the compound of the general formula (8), the general formula (9), the general formula (10) or the general formula (11) is contained in the photographic light-sensitive material, it is dissolved in water as an aqueous solution.
In the case of water insolubility, as a solution of alcohol (eg methanol, ethanol), esters (eg ethyl acetate), ketones (eg acetone) and other water-miscible organic solvent, silver halide emulsion solution or hydrophilic It may be added to the colloid solution. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, it can be used as a fine dispersion by a method known as a solid dispersion method.

Specific examples of the nucleation accelerator include JP-A-62-62.
-250439, compound examples IV-1 to IV-29, JP-A-5-273710, compound examples 1-29, U.S. Pat.
Compound Examples II-1 to II-17 of No. 847,180 and Compound Examples A-1 to A-47, B-1 of Japanese Patent Application No. 6-46604.
To B-21, C-1 to C-20 and the like.

Although gelatin is used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, other hydrophilic colloids can be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. In the present invention, the coating amount of gelatin as the binder is such that the total hydrophilic colloid layer on the side having the silver halide emulsion layer has a gelatin amount of 3 g / m ² or less and the total hydrophilic side on the side having the silver halide emulsion layer. total gelatin sex colloid layer and all hydrophilic colloid layers on the opposite surface is at 6 g / m ² or less, preferably 2.0 to 6.0 g / m ^2.

Using the silver halide light-sensitive material of the present invention,
In order to obtain photographic characteristics that are safe and have a safelight safety that can withstand bright room applications, use of the above-mentioned hydrazine derivatives and nucleation accelerators makes it possible to use conventional infectious developers and US Pat. No. 2,419,975. It is not necessary to use a highly alkaline developing solution close to pH 13 described in 1., but it is sufficient to use a developing solution stable at a lower pH. That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / liter or more of sulfite ion as a preservative by using the above-mentioned hydrazine derivative and nucleation accelerator, and has a pH of 9.5 to 11.
With a developer of 0, a super high contrast image can be obtained.

There are no particular restrictions on the development and fixing in the present invention, but it is preferable to use a dihydroxybenzene compound or reductone as the developing agent as the developing solution. Among these, a preferable developing solution in the case of using a dihydroxybenzene type developing agent has the following composition. (1) 0.2 to 0.75 mol / liter of dihydroxybenzene type developing agent, (2) 0.001 to 0.06 mol / liter of 1-phenyl-3-pyrazolidone type or p-aminophenol type auxiliary agent A developing agent, (3) 0.15 to 1.2 mol / liter of free sulfite ion, (4) a compound represented by the general formula (12), a compound represented by the general formula (12) and dihydroxybenzene The concentration ratio of the developing agent is 0.03 to 0.12
And a developer having a pH of 9.0 to 11.0,
Particularly, 9.5 to 10.7 is preferable. General formula (12)

[0109]

[Chemical 42]

In the formula, R ₁ and R ₂ each represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are It represents an atomic group which is bonded to each other to form a 5- to 8-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Y represents = 0 or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group.

Detailed description of the general formula (12) and specific compounds are described in Japanese Patent Application No. 5-282101. Of these, ascorbic acid and erythorbic acid (stereoisomers) are preferable. The addition amount of the compound of the general formula (12) is the concentration ratio of (the compound represented by the general formula (12) / hydroquinone-based developing agent) (the general formula (1
The value obtained by dividing the concentration of the compound represented by 2) by the concentration of the dihydroxybenzene-based developing agent) is in the range of 0.03 to 0.12. A preferable concentration ratio is 0.03 to 0.10. A particularly preferable concentration ratio is 0.05 to 0.09.

Examples of the dihydroxybenzene type developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone, but hydroquinone is particularly preferable. preferable. The concentration of the hydroquinone derivative in the developer is 0.2 to 0.75 mol / liter, preferably 0.2 to 0.5 mol / liter, particularly preferably 0.2 to 0.4 mol / liter. is there.

As the 1-phenyl-3-pyrazolidone derivative developing agent used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Trilyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like are preferable, and 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone are preferable.

As the p-aminophenol type developing agent used in the present invention, N-methyl-p-aminophenol, p
-Aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol, N- (4-hydroxyphenyl) glycine and the like, and among them, N-methyl-p-aminophenol is preferable. When the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
Mol / liter to 0.5 mol / liter, the latter of 0.0
It is preferably used in an amount of 6 mol / liter or less.

When a reductone is used as a developing agent, the reductone represented by the general formula (12) is used.
It is preferable to use the compound (1), and ascorbic acid or erythorbic acid (stereoisomer) is particularly preferable. In this case, as the auxiliary developing agent, the same ones as the dihydroxybenzene type developing agent can be used, and the p-aminofer type and / or 1-phenyl-3-pyrazolidone type auxiliary developing agent is preferable. When the compound of the general formula (12) is used as a developing agent, the general range of the amount used is 5 × 10 ⁻³ mol to 1 mol / liter of the developing solution.
The molar amount is particularly preferably from 10 ^-2 mol to 0.5 mol.

The preservative used in the developing solution preferred in the present invention is a free sulfite ion, and the form of addition to the developing solution includes sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and the like. The free sulfite ion concentration is 0.15 to 1.2 mol / liter,
It is preferably 0.3 to 1.0 mol / liter, and particularly preferably 0.3 to 0.8 mol / liter. The pH of the developer used in the developing treatment of the present invention is in the range of 9.0 to 11.0, preferably 9.5 to 10.7. Sodium hydroxide is used as the alkaline agent to set the pH.
It contains pH adjusters such as sodium carbonate, sodium triphosphate, potassium hydroxide, potassium carbonate, boric acid and the like.

In the developer used in the present invention, a dialdehyde type hardener or a bisulfite adduct thereof may be used. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α. -N-butoxyglutaraldehyde,
Examples include α, α-diethylsuccindialdehyde, butylmalein dialdehyde, or bisulfite adducts thereof. Of these, glutaraldehyde or its bisulfite adduct is most commonly used. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time is not significantly prolonged. Specifically, 1 to 50 g, preferably 3 to 1 liter of the developer is used.
It is 10 g.

An antifoggant is used in the developer used in the present invention, and examples thereof include indazole type, benzimidazole type and benztriazole type. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2
-Isopropyl-5-nitrobenzimidazole, 5-
Nitrobenztriazole, 4-[(2-mercapto-
1,3,4-thiadiazol-2-yl) thio] butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-2-thiol and the like can be mentioned.
The amount of these antifoggants is usually 0.01 to 10 mmol per liter of the developing solution, and more preferably 0.1 to 10 mmol.
It is 2 mmol. In addition to these organic antifoggants, for example, halides such as potassium bromide and sodium bromide can be used.

Further, various organic / inorganic chelating agents can be used in combination in the developing solution used in the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
As the organic carboxylic acid, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, acieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid , Itaconic acid, malic acid, citric acid,
Examples include tartar and the like, but the invention is not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitriloacetic acid, nitrilopropionic acid, ethylenediaminomonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriamine. Pentaacetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamino tetraacetic acid, etc. JP-A-52-25632, 55-67
No. 747, No. 57-102624, and Japanese Patent Publication No. 53-53
The compounds described in the specification of No. 40900 and the like can be mentioned.

As the organic phosphonic acid, US Pat.
4454, 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminotetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition to the above, Research Disclosure 18170, JP-A-57-208554 and 54 -61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730 and 54.
-112127, 55-4024, 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 ×, per 1 liter of the developing solution.
It is 10 ⁻³ to 1 × 10 ⁻² mol.

In addition to the above composition, the developer used in the present invention may optionally contain a buffering agent (eg, carbonate, alkanolamine), an alkaline agent (eg, hydroxide, carbonate),
Dissolution aids (eg polyethylene glycols, esters thereof), pH adjusters (eg organic acids such as acetic acid), development accelerators (eg US Pat. No. 2,648,604,
Various pyridinium compounds and other cationic compounds described in JP-B-44-9503 and US Pat. No. 3,171,247, cationic dyes such as phenosafranine,
Neutral salts such as thallium nitrate and potassium nitrate, JP-B-44
-9304, U.S. Pat.
No. 832, No. 2950970, No. 2577127, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, JP-B-44-950.
9, an organic solvent described in Belgian Patent 682862, a thioether compound described in U.S. Pat. No. 3,012,242, etc., particularly preferably a thioether compound), a surfactant and the like can be contained.

The development processing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the processing temperature is about 20 ° C. to about 50 ° C. and the processing time is 10 seconds to 2 minutes. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 400 ml or less, preferably 200 ml or less.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH.
Modifiers (eg ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
Examples thereof include amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added.
Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator,
For example, Japanese Examined Patent Publication Nos. 45-35754 and 58-12253.
5, thiourea derivatives described in JP-A Nos. 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat.
Examples include mesoionic compounds described in JP-A-229860, and compounds described in JP-A-2-44355 may be used. The pH of the fixer is preferably 4.0 to 6.5,
Particularly preferably, it is in the range of 4.5 to 6.0. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

The hardener in the fixing solution used in the present invention includes water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum.
The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is 600 ml / m ² or less, especially 300 ml / m ^{2 with} respect to the processing amount of the light-sensitive material.
It is preferably m ² or less.

The light-sensitive material that has been developed and fixed is then washed with water or stabilized. The washing or stabilizing treatment can be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. That is, not only is it possible to save water,
It is possible to eliminate the need for piping for the automatic processor. When the washing with water is carried out with a small amount of water, JP-A-63-18350 and JP-A-6-18350.
It is more preferable to provide a squeeze roller septic tank described in JP-A-2-287252. In addition, various oxidants may be added or filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Further, a part or the whole of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with anti-vibration means according to the process by the method of the present invention is disclosed in JP-A-60-
As described in No. 235133, it can also be used for a processing liquid having a fixing ability which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when a small amount of water is used and / or to prevent the treatment agent component attached to the squeeze roller from being transferred to the treated film. Good. Further, to prevent contamination by dyes eluted from a light-sensitive material, JP-A-63-16
The dye adsorbent described in No. 3456 may be installed in the washing tank.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and as an example, there is JP-A-2-201357.
The baths containing the compounds described in JP-A No. 2-132435, JP-A No. 1-125255, and JP-A No. 46-44446 may be used as the final bath of the light-sensitive material. In this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH buffers, hardeners, bactericides, fungicides, alkanolamines and surface active agents. As the water used for the agent, tap water, deionized water and halogen, ultraviolet germicidal lamps and various oxidizers (ozone,
It is preferable to use water sterilized by hydrogen peroxide, chlorate, etc.).

The treatment liquid preferably used in the present invention is preferably stored in the packaging material having low oxygen permeability described in JP-A-61-73147. On the other hand, in the case of reducing the replenishment amount, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area with the air in the processing tank. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,779 and 3,545,971 and the like.
It is possible to preferably use those comprising four steps of fixing, washing with water and drying. Further, the above treatment liquid may be used as a solid treatment agent. The solid processing agent preferably used in the present invention is powder, tablet, granule, powder, lump or paste, and the preferred form is JP-A-61-2599.
The form or tablet described in No. 21. The method for producing tablets is described in, for example, JP-A Nos. 51-61837 and 54-155.
038, 52-88025, British Patents 1,21
It can be produced by a general method described in No. 3,808,
Further, the granule treating agent is, for example, JP-A No. 2-109042,
2-109043, 3-39735 and 3-
It can be produced by a general method described in No. 39739 or the like. Furthermore, powder treating agents are disclosed in, for example, JP-A-54-133.
No. 332, British Patents 725,892 and 729,86.
No. 2 and German Patent No. 3,733,861 and the like, but can be produced by a general method.

The bulk density of the solid processing agent preferably used in the present invention is preferably 0.5 to 6.0 g / cm ³ , particularly from the viewpoint of its solubility and the effect of the object of the present invention. It is preferably 1.0 to 5.0 g / cm ³ .

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and spectral enhancement described in JP-A Nos. 1-112235, 2-124560, 3-79928, 5-11389, and Japanese Patent Application No. 3-411064. Sensitive dye. 2) Surfactants, antistatic From JP-A-2-12236, page 9, upper right column, line 7 or the same, from antistatic agent, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column, line 18. 3) Antifoggant, Stability JP-A-2-103536, page 17, lower right column 19, agent line to page 18, upper right column, line 4 and lower right column, line 1 to line 5. Further, thiosulfinic acid compounds described in JP-A-1-237538. 4) Compound having an acid group From JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A 2-55349, page 8, lower right column, line 13 Page 11, upper left column, line 8. 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 7) Dye JP-A-2-103536, page 17, lower right column, line 1 to line 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 Dyes described in Kaihei 2-294638 and JP-A-63-296039. Further, solids described in WO88 / 04794, European Patent No. 456148, JP-A-5-11382, Japanese Patent Application No. 5-224717, Japanese Patent Application No. 6-117454, and the like. Disperse dye. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Redox compounds Compounds represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and general compounds described in pages 3 to 20 of JP-A 3-174143. Formulas (R-1), (R-2), (R-3), Compound Examples 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 11) Monomethine compound A compound of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to items, page 12, lower left column, and European Patent No. 452,772A.

[0132]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto. Example 1 <Emulsion preparation> Emulsion A; 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per ⁵ mol of sodium chloride and silver kept at 40 ° C., 5 × 10 ⁻³ mol of 4-hydroxy-6-methyl-
PH containing 1,3,3a, 7-tetrazaindene = 2.
0 in a 1.5% gelatin aqueous solution and an aqueous solution of silver nitrate and 1.5 × 10 ⁻⁶ mol of (NH ₄ ) ₂ Rh (H ₂
O) Cl ₅ containing sodium chloride solution was simultaneously added by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds to half the amount of silver in the final particles, and the core particles had a particle diameter of 0.12 μm.
Was adjusted. Then, an aqueous solution of silver nitrate and 4.5 × 10 ⁻⁶ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl per mol of silver were added.
A sodium chloride aqueous solution containing ₅ was added in the same manner as above for 7 minutes to prepare silver chloride cubic particles having an average particle size of 0.16 μm. (Coefficient of variation: 12%) After that, the product was washed with water by a flocculation method well known in the art to remove soluble salts, and then gelatin was added. Compound-F and phenoxyethanol were added as 1 mol of silver as a preservative without chemical ripening. 60 mg each, stabilizer 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver. (As final particles, pH =
5.7, pAg = 7.5, Rh = 3 × 10 ⁻⁶ mol / Ag
It became a mole. )

Emulsion B: Grain formation, washing with water and addition of gelatin were carried out in exactly the same manner as in Emulsion A, pH was adjusted to 5.7 and pAg was adjusted to 7.5, and 2 × 10 ^-5 mol of thiol was added per mol of silver. After adding sodium sulfate, the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and then the stabilizer and the preservative were added in the same manner as in the emulsion A.

Emulsion C: Grain formation, washing with water and addition of gelatin were carried out in the same manner as in Emulsion A, pH was adjusted to 5.7 and pAg was adjusted to 7.5, and 1 × 10 ^-5 mol of chloride was added to 1 mol of silver. After the addition of gold acid, the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and then a stabilizer and a preservative were added in the same manner as in Emulsion A.

Emulsion D: The amount of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ doped in grain formation was 7 × 10 _5.
^-6 (core: shell dope ratio = 1: 3), except for the same as in emulsion A, grain formation, washing with water, addition of gelatin, and pH
= 5.7, pAg = 7.5, 1 × 10 ⁻⁵ mol of chloroauric acid and 7 × 10 ⁻⁵ mol of sodium thiosulfate were added per mol of silver, and the mixture was kept at 60 ° C. for 60 minutes. Heat
After chemical sensitization, stabilizers and preservatives were added as in Emulsion C.

Emulsion E: Grain formation, washing with water and addition of gelatin were carried out in exactly the same manner as in Emulsion D, pH was adjusted to 5.7 and pAg was adjusted to 7.5, and 1 × 10 ^-5 mol of chloride was added per mol of silver. Auric acid, 5 × 10 ⁻⁶ mol of sodium thiosulfate, and 5 ×
After 10 ⁻⁶ mol of selenium sensitizer SE-4 was added, the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and then the stabilizer and preservative were added in the same manner as in Emulsion D.

Emulsion F: The metal species doped in grain formation is K ₂ Ru (NO) Cl ₅ , and the dope amount is 3.5 × 10 ^-6 mol / Ag mol and the grains are uniformly doped in equal amounts. Except for the above, the same preparation as in Emulsion E was made.

Emulsion G: The metal species doped in grain formation is K ₂ Ru (H ₂ O) Cl ₅ , and the doping amount is 5 × 10 ^-6 mol / Ag mol, and the grains are uniformly doped. Except for the above, the same preparation as in Emulsion E was made.

Emulsion H; the amount of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ doped in grain formation is 5 × 10 5.
^-5 (core: shell dope ratio = 1: 3) was prepared in exactly the same manner as Emulsion E. <Preparation of Emulsion Layer Coating Solution and Its Coating> The following compounds were added to the emulsions shown in Table 1, and the gelatin coating amount was 0.9 g / m ² and the coating silver amount was 2. on the following support including the undercoat layer. A silver halide emulsion layer was coated so as to have a weight of 7 g / m ² . Emulsion layer coating solution 1-phenyl-5-mercaptotetrazole 10 mg / m ² 3- (5-mercaptotetrazole) -sodium benzenesulfonate 11 mg / m ² N-oleyl-N-methyltaurine sodium salt 19 mg / m ² compound- A 20 mg / m ² compound-B ₁ 13 mg / m ² compound-B ₂ 15 mg / m ² compound-C 70 mg / m ² ascorbic acid 1 mg / m ² acetic acid Amount at which the film surface pH is 5.2 to 6.0 Compound -D 1 g / m ² ribolane-1400 (manufactured by Lion Oil & Fats Co., Ltd.) 50 mg / m ² compound-E (hardener) Amount at which the swelling ratio in water is 80% (adjusted to pH = 5.6) The nucleating agent was applied as shown in Table 1.

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer. <Preparation of Emulsion Protecting Lower Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 0.8 g /
It was applied so as to be m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.8 g / m ² compound F 1 mg / m ² 1,5-dihydroxy-2-benzaldoxime 14 mg / m ² C ₂ H ₅ SO ₂ SNa 3 mg / m ² compound H 20 mg / M ² compound C 3 mg / m ² compound I 200 mg / m ² sodium p-dodecylbenzenesulfonate 7 mg / m ² compound G 20 mg / m ²

<Preparation of Emulsion Protecting Upper Layer Coating Liquid and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the gelatin coating amount would be 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.45 g / m ² amorphous silica matting agent (average particle size 4.4 μm) 40 mg / m ² amorphous silica matting agent (average particle size 3.6 μm) 10 mg / m ² compound F 1 mg / m ² compound C 8 mg / m ² solid disperse dye -G ₁ 68mg / m ² Liquid paraffin 21 mg / m ² N-perfluorooctane sulfonyl -N- propyl glycine Potassium 5 mg / m ² p-dodecylbenzenesulfonate Sodium 29 mg / m ²

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

<Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 0.
It was applied so that the amount would be 06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 186 mg / m ² gelatin (Ca ⁺⁺ content 2700 ppm) 0.06 g / m ² sodium p-dodecylbenzenesulfonate 13 mg / m ² dihexyl- α-sulfosuccinate sodium 12 mg / m ² compound C 12 mg / m ² compound F 1 mg / m ²

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94mg / m ² Polymethyl methacrylate fine particles (average particle size 4.7μ) 7mg / m ² Compound J 233 mg / m ² Compound K 21 mg / m ² Compound G 146 mg / m ² Compound F 3mg / m ² p- sodium dodecylbenzenesulfonate 68 mg / m ² dihexyl -α- sulfosuccinates sodium _{^{21mg / m 2 C 8 F 17}} SO 3 Li 4mg / m 2 N- perfluorooctane sulfonyl -N- propyl glycine amount Potajiumu 6 mg / m ² sodium sulfate 177 mg / m ² compound -E (hardener) swelling rate in water is 90%

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated with the first and second undercoat layers having the following compositions on both sides. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-M 0.20 g Colloidal silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. The dry film thickness was 0.
It was applied so as to be 9μ.

<Undercoat Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-L 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-F 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm. Sample 1
16 was produced.

[0147]

[Chemical 43]

[0148]

[Chemical 44]

[0149]

[Chemical formula 45]

<Coating method> On the support having the above-mentioned undercoat layer, first, from the side closer to the support as the emulsion surface side, the emulsion layer, the emulsion protection lower layer, and the emulsion protection upper layer were successively held at 35 ° C in a slide hopper. Simultaneous multi-layer coating while adding a hardener solution according to the method and passing through a cold air set zone (5 ° C), and then the conductive layer and the back layer in this order from the side closer to the support on the side opposite to the emulsion side. Simultaneous multi-layer coating was performed by adding a hardener solution by a slide hopper method, and a cold air set zone (5 ° C.) was applied. The coating liquid exhibited sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after applying the back surface side, it was conveyed in a state in which there was no contact with the roller and the rest until winding. The coating speed at this time was 120 m / min.

<Drying conditions> After setting, the product was dried with a drying air at 30 ° C. until the weight ratio of water / gelatin reached 800%, and 8
Dry 0 to 200% with 35 ° C 30% dry air, apply the air as it is, and after 30 seconds from the time when the surface temperature reaches 34 ° C (assuming that the drying is completed), dry with 48 ° C 2% air for 1 minute. did. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800% and 3 seconds from 800 to 200%.
5 seconds, 5% from 200% to completion of drying.

This sensitive material was wound up at 40 ° C. at 23 ° C., then cut in the same environment and placed in a barrier bag conditioned for 6 hours to give 4
After the humidity was controlled at 0 ° C. and 10% for 8 hours, the sample was sealed together with the thick paper that was controlled at 23 ° C. and 40% for 2 hours to prepare the samples shown in Table 1. When the humidity in the barrier bag was measured, it was 40%.

<Evaluation Method> To evaluate the extracted character image quality, Japanese Patent Publication No. 28-85
No. 6 No. 6 original document "Transparent embedding base / film having line image positive image formed (line image original) / transparent embedding base / film having dot image formed (mesh) Point original), and the emulsion surface of each sample are brought into close contact with each other and exposed by a P-627FM printer manufactured by Dainippon Screen Co., Ltd.
Fuji Photo Film Co., Ltd. automatic processor FG-680AG
And the developer 1 for 20 seconds at 38 ° C., fixing, washing with water, and drying. The fixer used was fixer 1. Also, DIA Rayon P-manufactured by Mitsubishi Rayon Co., Ltd. between the light source and the sample during exposure.
A 1003 mm-thickness (transmittance at 393 nm of 50%, a filter that absorbs light on the shorter wavelength side and transmits light on the longer wavelength side than that) was placed and exposed.

Practical Dmax 50% halftone originals described in the evaluation of the character image quality without Dmax were exposed on a film sample so that the halftone dot area was 50%, and two sets of samples were prepared. One set was treated with the developer 1 (new solution), and the other set was treated with the fatigue solution of the developer 1. The fatigue solution was obtained by treating the developer solution 1 with a developer replenishment amount of Taizen (0.31 m ² ) of 50 cc per sheet and 50 m ² per day for 5 days. (The processing condition is 38 ° C. for 20 seconds, the blackening rate is 20%,
Replenishment of fixer is 50cc per sheet.

[0155] (Developer 1)   Potassium hydroxide 40.0g   Diethylenetriamine-pentaacetic acid 2.0 g   Potassium carbonate 60.0g   Sodium metabisulfite 70.0g   Potassium bromide 7.0g   Hydroquinone 40.0g   5-methylbenzotriazole 0.35 g   4-hydroxymethyl-4-methyl-1-phenyl-3-     Pyrazolidone 1.50g   2-Mercaptobenzimidazole-5-sulfonic acid     Sodium 0.30g   3- (5-mercaptotetrazol-1-yl) ben     Sodium zensulfonate 0.10 g   Sodium erythorbate 6.0 g   5.0 g of diethylene glycol   Add potassium hydroxide and add water to 1 liter   Adjust the pH to 10.65. 1 liter (Fixer 1)   Ammonium thiosulfate 119.7 g   Ethylenediaminetetraacetic acid 2Na dihydrate 0.03g   Sodium thiosulfate pentahydrate 10.9g   Sodium sulfite 25.0g   12.4g of NaOH (in pure content)   Glacial acetic acid 29.1g   Tartaric acid 2.92g   Sodium gluconate 1.74g   Aluminum sulfate 8.4g   pH (adjusted with sulfuric acid or sodium hydroxide) 4.8   1 liter with water

The obtained results are shown in Table 1. As is apparent from Table 1, the samples (7, 13 to 18) of the present invention are excellent in the image quality of extracted characters, and the variation in the practical Dmax between the new liquid and the fatigue liquid is small. Samples using an emulsion subjected to gold-sulfur sensitization or gold-sulfur selenium sensitization are particularly excellent in the image quality of extracted characters, and practical Dmax
The fluctuation is also small.

[0157]

[Table 1]

Example 2 Instead of K ₂ Ru (NO) Cl ₅ of Emulsion F prepared in Example 1, K ₂ Ir (NO) Cl ₅ or K ₃ Cr (CN) was used.
Example ₆ was used to make Emulsions I and J, Sample 17 of Example 1
A sample was prepared in the same manner as above and evaluated in the same manner as in Example 1. The result was similar to that of Sample 17 of Example 1.

Example 3 The sample prepared in Example 1 was prepared by dissolving the developing solution 2 and the fixing solution 2 which are the solid processing agents described below in the manufacturing method and storing form for the developing solution and the fixing solution in water to obtain a final amount of 10 liters. The sample of the present invention was excellent in the image quality of extracted characters and the result of the variation in the practical Dmax between the new solution and the fatigue solution was small, as in Example 1.

The method for producing a solid developer is as follows. A container made of high-density polyethylene (average wall thickness = 500 μm, partially 200-1000 μm) is packed with 10 liters of developing components as a working solution in solid form. It was At this time, the components were mixed and then filled in a container. Developer liquid 1
Table 2 shows the composition of 0 liter and the form of the raw material.

[0161]

[Table 2]

Here, in the raw material form, the bulk powder was used as it was as a general industrial product, and commercially available products were used for both beads and pellets of the alkali metal salt. When the raw material form was briquette, it was pressed and compressed using a briquetting machine to prepare an irregular rugby ball shape having a length of about 4 to 6 mm, which was crushed and used. For minor components, each component was blended before briquetting. The fixing solution is made of high-density polyethylene for the solid agent part and the liquid agent part as follows (thickness average = 500 μm, width 200-1000 μm).
What was filled in the container of m) was used. 1 volume after dissolution
The pH was 4.85 with 0 liter. When the developer replenishment rate is 160 ml / m ² during running, the fixing solution replenishment rate is 240 ml / m ² , and the developer replenishment rate is 10
When 0 ml / m ² was used in the replenishment rate = 150 ml / m ² of the fixing solution.

[0163] <Solid agent part>   Ammonium thiosulfate 1200g   Sodium thiosulfate 150g   400 g of sodium acetate   Sodium metabisulfite 200g <Liquid part>   Aluminum sulfate (27%) 300g   Sulfuric acid (75%) 30g   Sodium gluconate 20g   EDTA 0.3g   Citric acid 40g   The solid agent parts are mixed and filled.

Example 4 The sample prepared in Example 1 was treated with the following developing solution 3. However, like Example 1, the sample of the present invention was excellent in the image quality of the extracted characters, and was composed of a new solution and a fatigue solution. The result that the fluctuation of the practical skill Dmax was small was obtained. (Fixer 1 was used as the fixer.)
As for the fatigue solution, the developer 3 is added to the developer replenishment amount (0.31 m ² ) 1
It was processed for 50 cc per sheet and 50 m ² per day for 2 days. (Treatment condition is 38 ° C for 20 seconds, blackening rate is 2
0%, fixer replenishment is 50cc per sheet)

[0165] <Developer 3>   1.71 g of sodium hydroxide   Diethylenetriamine-5 acetic acid 4 g   27.5g potassium carbonate   Sodium carbonate 25.5g   Sodium erythorbate 30g   N-methyl-p-aminophenol 7.5 g   KBr 2g   5-methylbenzotriazole 0.1 g   1-phenyl-5-mercaptotetrazole 0.02 g   Sodium sulfite 5g   Glacial acetic acid 9g   Add water to 1 liter and adjust the pH to 9.8.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03C 5/29 501 G03C 5/29 501 5/31 5/31 (56) Reference JP-A-7-234472 (JP, A) JP-A-5-333467 (JP, A) JP-A-7-43867 (JP, A) JP-A-63-294552 (JP, A) JP-A-6-317886 (JP, A) JP-A-6-347954 (JP, A) JP 7-72570 (JP, A) JP 7-128814 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C03C 1/06 501 C03C 1 / 035,1 / 09 C03C 5/29 501 C03C 5/31

Claims (4)

(57) [Claims] 1. A development treatment of a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support.
A silver halide emulsion layer comprising Ir, Ru, R
containing at least 1 × 10 ⁻⁶ mol of a heavy metal ion selected from h, Re, and Cr per mol of silver halide,
It comprises chemically sensitized silver content of 95 mol% or more silver halide grains chloride by a gold compound and a sulfur compound, in the following general formula (1) at least one layer of the emulsion layer and / or other hydrophilic colloid layer R ₂ is a hydrogen atom
At least one hydrazine derivative and the following general formula
In (1), R ₂ is an alkyl group, an aryl group, or unsaturated
Heterocyclic group, alkoxy group, aryloxy group, amino
Of hydrazine derivatives that are hydrazine or hydrazino groups
Silver halide photographic image containing one kind and a nucleation accelerator
Light materials, development method for processing a silver halide photographic light-sensitive material characterized that you treated with pH11.0 following developer. General formula (1) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ is -CO- group, -SO ₂ -
Group, —SO— group, embedded image Represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group, and A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted Represents an arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the group defined for R ₂ ,
It may be different from R ₂ . 2. The silver halide grain is further chemically sensitized with a selenium compound.
The method for developing and processing a silver halide photographic light-sensitive material as described in 1 . 3. The silver halide emulsion is Ir, Ru, R.
The silver halide photographic light-sensitive material according to claim 1 or 2, wherein a heavy metal ion selected from h, Re and Cr is contained in an amount of 1 x 10 ^{-6 to} 3 x 10 ^-5 mol per mol of silver halide. Material development processing method . 4. The silver halide according to any one of claims 1, 2, 3 The silver halide photographic light-sensitive material, the replenishment rate of the developing solution is characterized that you treated with 200 ml / m ² or less Development processing method of photographic light-sensitive material.