JPH09152687A - Processing agent for silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a processing agent for silver halide photographic sensitive materials prepd. by using ascorbic acid which is good to environment and has high safety and its deriv. into a main chemical for developing by incorporating a specific compd. into the processing agent and incorporating a redox compd. which releases a development restrainer when oxidized into the agent. SOLUTION: The compd. expressed by formula is incorporated into the processing agent having the silver halide photographic sensitive materials having at least one layer of silver halide emulsion layers on one surface of a base without substantially incorporating hydroquinone into the compd. In addition, the redox compd. which releases the development restrainer when oxidized is incorporated therein. In the formula, R1 , R2 respectively independently denote a substd. or unsubstd. (alkyl group, amino group, alkoxy group, alkylthio group); R1 and R2 may form a ring by bonding to each other; (k) denotes 0 or 1; X denotes -CO- or -CS- when k=1; M1 , M2 respectively denote hydrogen atoms or alkaline metals.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for silver halide photographic light-sensitive materials and a processing method using the same, and it is possible to remarkably improve halftone dot reproducibility, particularly missing of large dots. The present invention relates to a silver halide photographic light-sensitive material processing agent and a processing method using the same.

[0002]

2. Description of the Related Art Conventionally, in developing processing of a silver halide photographic light-sensitive material, processing by an automatic developing machine has been frequently used from the viewpoint of stability, quickness, simplicity and handleability. Further, in most cases, hydroquinone has been used as a developing agent in a developing solution used for developing a black-and-white light-sensitive material. Under the present circumstances, it has been used for the development of most black and white light-sensitive materials from the viewpoints of photographic activity, stability, easy availability, handleability, and cost. However, hydroquinone has a problem in that the developer is blackened by oxidation of air or the like, and that what is polymerized and adhered to a roller or the like in an automatic developing machine adheres to a photosensitive material to deteriorate the finish.

Further, since environmental protection has been appealed on a global scale in recent years, there has been a strong demand in the industry for the development of more environmentally friendly products and systems.

At present, various studies have been actively conducted to solve these problems, and some results have been reported. In particular, there have been many studies using ascorbic acid as a developing agent as a substitute for hydroquinone, and for example, US Pat.
There are reports such as No. 36,816 and WO93 / 11456.

However, the developing performance of the developing solution using the developing agent described in the above patent causes a problem that halftone dot reproducibility, in particular, missing of large dots is insufficient as compared with the developing solution of hydroquinone developing agent. , Further improvement is desired.

As described above, in the development in the system which does not use hydroquinone, there is still no report of the research result which can meet the demand.

[0007]

SUMMARY OF THE INVENTION The object of the present invention has been made in view of the above circumstances, and is a silver halide photographic light-sensitive material using ascorbic acid and its derivatives which are environmentally friendly and highly safe as a developing agent. Providing a treating agent for materials,
Another object of the present invention is to provide a processing method of a silver halide photographic light-sensitive material in which halftone dot reproducibility, in particular, omission of large dots is remarkably improved by processing with a developing solution containing the processing agent.

[0008]

The above objects of the present invention have been attained by the following constitutions.

(1) In a processing agent for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one surface of a support, the following general formula ( A processing agent for silver halide photographic light-sensitive materials, comprising a redox compound containing the compound represented by 1) and releasing a development inhibitor when oxidized.

[0010]

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In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted (alkyl group, amino group, alkoxy group, alkylthio group), and R ₁ and R ₂ are bonded to each other to form a ring. You may form. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

(2) A method for treating a silver halide photographic light-sensitive material, which comprises treating the silver halide photographic light-sensitive material with the above-mentioned processing agent for silver halide photographic light-sensitive material.

The present invention has been a conventional concern in a method for processing a silver halide photographic light-sensitive material by using it in combination with a specific redox compound in a system using ascorbic acid and its derivative as a developing agent as a processing agent. This has an effect of remarkably improving dot reproducibility, particularly omission of large dots.

Hereinafter, the present invention will be described specifically.

First, the compound represented by the general formula (1) will be described.

In the compound represented by the general formula (1), a compound represented by the following general formula [1-a] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0017]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted (alkyl group, aryl group, amino group, alkoxy group), sulfo group, carboxyl group, amide group or sulfonamide group, and Y ₁ represents O. Or S, and Y ₂ represents O, S, or NR ₄ . R ₄ is a substituted or unsubstituted (alkyl group,
Represents an aryl group). M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in formula (1) or [1-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula (1) or the general formula [1-a] are shown below, but the invention is not limited thereto.

[0021]

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[0022]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof (eg potassium, sodium) or derivatives derived from them, and they are available as commercial products or easily known synthetic methods. Can be synthesized by.

The processing agent according to the present invention is characterized by containing substantially no dihydroxybenzene type developer. The dihydroxybenzene-based developer mentioned here is represented by the following general formulas V-1 to V-3.

[0025]

[Chemical 6]

In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a halogen atom or a sulfo group.

Specific compounds include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
Although 5-dimethylhydroquinone and the like, hydroquinone has been most commonly used.

In the present invention, these dihydroxybenzenes are not substantially contained, and substantially no dihydroxybenzenes are contained, or 0.09 per liter of the developing solution is contained.
It means that it is contained in an amount of less than 1 mol, but in the present invention, it is preferably not contained at all.

Next, the redox compound which is added to the developer and can release the development inhibitor by being oxidized will be described below.

Examples of redox compounds include hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines and reductones as redox groups. Preferred redox compounds are compounds having a -NHNH- group as a redox group and compounds represented by the following general formulas [3] to [8].

The compound having a --NHNH-- group as a redox group is represented by the following general formula [RE-a] or [RE-
b] is mentioned.

General formula [RE-a] T-NHNHCOV- (Time) -PUG General formula [RE-b] T-NHNHCOCOV- (Time) -PUG In the formula, T and V may each be substituted (aryl). Group or alkyl group). The aryl group represented by T and V contains a benzene ring or a naphthalene ring, and this ring may be substituted with various substituents, and a preferable substituent is a linear or branched alkyl group (preferably having a carbon number). 2 to 2
0, for example, methyl, ethyl, isopropyl group, dodecyl group, etc., alkoxy group (preferably having 2 to 21 carbon atoms)
Examples thereof include a methoxy group, an ethoxy group, etc., an aliphatic acylamino group (preferably having an alkyl group having 2 to 21 carbon atoms, such as an acetylamino group, a heptylamino group, etc.), an aromatic acylamino group, etc. In addition to these, a substituted or unsubstituted aromatic ring as described above is-
CONH -, - O -, - SO 2 NH -, - NHCONH
Also included are those linked by a linking group such as —, —CH ₂ CHN—. Examples of the photographically useful group include 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole and 5-nitroindazole.
Examples thereof include nitrobenztriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4-nitroimidazole and the like. These development inhibitor compounds are TN
It can be directly connected to the CO site of HNH-CO- via a heteroatom such as N or S or via an alkylene, phenylene, aralkylene or aryl group and further via a heteroatom such as N or S. In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2-
(Dodecylethylene oxide thiopropionic acid amide-5- (5-nitroindazol-2-yl) hydroquinone, 2- (stearylamide) -5- (1-phenyltetrazole-5-thio) hydroquinone, 2-
(2,4-di-t-amylphenopropionic acid amide-
Examples thereof include 5- (5-nitrotriazol-2-yl) hydroquinone and 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone.

These redox compounds are described in US Pat.
It can be synthesized with reference to the description of No. 269,929. The amount added is in the range of 1 × 10 ⁻³ to 1 × 10 ⁻¹ mol / l.

Among the compounds represented by the general formula [RE-a] or [RE-b], particularly preferable compounds are listed below.

[0035]

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[0036]

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Specific examples of other preferable redox compounds include R-1 to R-50 described in JP-A-4-245243, page 236 (8), page "0053" to 250 (22), page "0068". Can be mentioned.

The redox compounds represented by the following general formulas [3] to [8] will be described.

[0039]

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[0040]

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In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₄ represents a hydrogen atom. R ₅ to R ₉ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃ represent a substituent capable of substituting on the benzene ring. X ₁ and X ₂ are O or N
Represents H. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W represents N (R ₁₀ ) R ₁₁ or OH, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. COUP represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and represents a coupling site of the coupler. T
m represents a timing group. m ₁ and p ₁ represent an integer of 0 to 3. q ₁ represents an integer of 0 to 4. n represents 0 or 1. PUG represents a development inhibitor.

The compounds represented by the general formulas [3] to [8] will be described.

An alkyl group represented by R ₁ and R _{5 to} R ₁₁ ;
The aryl group and the heterocyclic group are preferably methyl group, p
-Methoxyphenyl group, pyridyl group and the like can be mentioned. R
_{Among the} acyl group, carbamoyl group, cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group represented by ₂ and R ₃ , preferably an acyl group and carbamoyl group. And a cyano group. The total number of carbon atoms in these groups is 1
It is preferably -20. R _{1 to} R ₁₁ may further have a substituent, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group). , Methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, Naphthyl group, p-tolyl group, p-chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group ( For example, acetylamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group, ether Thio group, butylthio group, etc.), an arylthio group (e.g., phenylthio group), a sulfonylamino group (e.g., methanesulfonylamino group, etc. benzenesulfonylamino group), a ureido group (e.g., 3-methylureido group, 3,
3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl Group (eg ethylsulfamoyl group, dimethylsulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group) Group, butanesulfonyl group, phenylsulfonyl group etc.), acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group, dimethylamino group etc.), hydroxyl group, nitro group, Bromide group (e.g. phthalimido group), a Hajime Tamaki (e.g., pyridyl, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group).

Examples of the coupler residue represented by COUP include the following. Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, and indazolone couplers. Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler.
Colorless coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolinone, thiazolinone, etc.). Further, among the coupler residues represented by COUP, those preferably used in the present invention include:
It can be represented by the general formula (COUP-1) to the general formula (COUP-8).

[0045]

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In the formula, R ₁₆ represents an acylamido group, anilino group or ureido group, and R ₁₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0047]

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In the formula, R ₁₈ and R _{19 each} represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfoulide group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₂₀ and R ₂₁ each represent a fatty acid. It represents a group group, an aromatic group or a heterocyclic group. Further, one of R ₂₀ and R ₂₁ may be a hydrogen atom. a is an integer of 1 to 4, b is 0 to 5
Represents an integer. When a and b are plural, R ₁₈ or R ₁₉ may be the same or different.

[0049]

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In the formula, R ₂₂ represents a tertiary alkyl group or an aromatic group, and R ₂₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₄ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom or a sulfonamide group.

[0051]

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In the formula, R ₂₅ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ₂₆ represents a hydrogen atom, a halogen atom or a nitro group.

[0053]

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R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

The 5- or 6-membered heterocycle represented by Z ₁ may be a single ring or a condensed ring, and is a 5- or 6-membered heterocycle having at least one of O, S and N atoms in the ring. Is mentioned. These rings may have a substituent, and specific examples thereof include the above-mentioned substituents.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,3.
No. 23, or No. 3,674,478, Research
Disclosure 21228 (December 1981)
Month), or JP-A-57-56837 and JP-A-4-43.
No. 8 and the like.

Preferred development inhibitors for PUG include, for example, US Pat. No. 4,477,563 and JP-A-60-218.
No. 644, No. 60-221750, No. 60-2336
No. 50, or the development inhibitor described in No. 61-11743.

The general formula [3] to be used in the present invention will be described below.
Specific examples of the compound represented by [8] are listed, but the present invention is not limited thereto.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The amount of the redox compound represented by the above general formulas [3] to [8] added is in the range of 1 × 10 ^-3 to 1 × 10 ^-1 mol / l.

In the present invention, the hydrazine derivative is preferably a compound represented by the following general formula [H].

[0069]

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In the formula, A represents an aryl group or a heterocycle containing at least one sulfur atom or oxygen atom, and G represents-.
(CO) _n -group, sulfonyl group, sulfoxy group, -P
(═O) R ₂ — group or iminomethylene group, n represents an integer of 1 or 2, and both A ₁ and A ₂ are hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted (alkyl). A sulfonyl group, an acyl group), R is a hydrogen atom,
Each substituted or unsubstituted alkyl group, alkenyl group,
Represents an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, an amino group, a carbamoyl group, or an oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like.

Of the compounds represented by the general formula [H], the compounds represented by the following general formula [Ha] are more preferred.

[0072]

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In the formula, R ¹ is an aliphatic group (eg octyl group, decyl group), aromatic group (eg phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg pyridyl group, cenyl group, Represents a furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one diffusion resistant group or silver halide adsorption promoting group.

The anti-diffusion group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is an alkyl group having 8 or more carbon atoms and relatively inert to photographic properties. , Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

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

In the general formula [Ha], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and —CON (R ⁴ )
(R ⁵⁾ groups (R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group,
R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

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

[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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Specific examples of other preferable hydrazine derivatives include US Pat. No. 5,229,248, Nos. 4-6.
(1) to (252) described in the 0th column.

The hydrazine derivative can be synthesized by a known method, for example, US Pat. No. 5,229,248.
It can be synthesized by the method described in columns 59 to 80.

The addition amount may be any amount as long as it causes a high contrast (a high contrast amount), and the grain size of the silver halide grains, the halogen composition,
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
It is in the range of ^-1 mol, preferably in the range of ^10-5 to ^10-2 mol.

The hydrazine derivative is added to the silver halide emulsion layer or its adjacent layer.

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

[0091]

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

Specific examples of these nucleation accelerators [Na] will be given below.

[0094]

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[0095]

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[0096]

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[0097]

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

Specific examples of the compound represented by the general formula [Nb] include the following.

[0100]

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[0101]

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Specific examples of other preferable nucleation promoting compounds are described in JP-A-6-258751, page (13), “0062”.
~ (15) page "0065" (2-1)
To (2-20) and 6-258751 (1
5) Pages “0067” to (16) “3-1 to 3-6” described in “0068”.

These nucleation accelerating compounds can be used in any layer on the silver halide emulsion layer side, but are preferably used in the silver halide emulsion layer or a layer adjacent thereto.

Next, the pyridinium salt compound will be described.

Examples of the pyridinium salt compound include pyridinium salts and their derivatives, quinolinium salts and their derivatives, and isoquinolinium salts and their derivatives (hereinafter, these pyridinium salts and their derivatives are simply referred to as pyridinium salt derivatives). it can.

The pyridinium salt derivative used in the present invention includes a pyridinium salt derivative represented by the following general formula (NI), a quinolinium salt derivative represented by the general formula (N-II) and a general formula (N- Examples include isoquinolinium salt derivatives represented by III).

[0107]

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In the formula, R ₁ is an amino group, an alkyl-substituted amino group (N-methylamino group, N, N-dimethylamino group or the like), an aromatic group such as a phenyl group or a pyridyl group, or
Represents AZ. A represents an alkylene group having 1 to 20 carbon atoms or —CH ₂ CH═CHCH ₂ —, Z is a hydrogen atom, an optionally substituted phenyl group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, Acyl group such as benzoyl group and acetyl group, alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group, cyano group, N-alkylamide group, amide group or general formula (N
Represents a group represented by -Ia).

[0109]

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General formula (N-I) and general formula (N-Ia)
Where R ₂ is a lower alkyl group ( _2- hydroxy group, _2- methyl group, ethyl group, propyl group, butyl group, etc.), which is substituted with an aromatic group such as a hydroxyl group, an alkoxy group, a phenyl group or a pyridyl group. Ethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 4-ethoxybutyl group, benzyl group, 2-phenylethyl group, 3- (4
-Pyridyl) propyl group), amide group (-CONH
₂ represents -CONHCH _3, etc.) or an optionally substituted amino group _{(-NH 2, -NHSO 2 C 5} H 11, such as -NHSO ₂ Ph). n1 represents 0, 1, 2 or 3. However,
When a plurality of R ₂ 's are present, they may be different from each other. X ⁻ is iodine ion, bromine ion, chlorine ion, p-toluenesulfonate ion, perchlorate ion,
Represents an anion such as methylsulfate. However, X does not exist when the general formula (NI) has a betaine structure.

[0111]

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In the formula, R ₃ represents a substituted or unsubstituted lower alkyl group, alkenyl group or alkynyl group. As the substituent, a hydrogen group, a lower alkoxy group such as a methoxy group and an ethoxy group, an aromatic group such as a phenyl group, an acyl group such as an acetyl group and a benzoyl group, an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, an amide A group and a cyano group are preferred. Specific examples of R ₃ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, 2
-Hydroxyethyl group, 3-hydroxypropyl group, 2
-Methoxyethyl group, 3-ethoxypropyl group, 2-phenylethyl group, 3-acetylpropyl group, 2-benzoylethyl group, 2-methoxycarbonylethyl group, 2-
Examples thereof include a cyanoethyl group, a 2-carbamoylethyl group, a butenyl group, a propargyl group, a benzyl group, a toluyl group and a phenethyl group. R ₄ and R ₅ are each independently a halogen atom, a lower alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, isobutyl group, pentyl group, etc.), substituted lower alkyl group or lower alkoxy group (eg, methoxy group, ethoxy group, etc.).

The substituent of the substituted lower alkyl group is preferably a hydroxyl group, a lower alkoxy group, or a substituted or unsubstituted aromatic group (eg, phenyl group, alkyl-substituted phenyl group, etc.). Specific examples of the substituted lower alkyl group include, for example, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, benzyl group, 2-phenylethyl group, 2 -A tolylethyl group etc. can be mentioned. n2 and n3 each independently represent 0, 1 or 2. When at least one of R ₄ and R ₅ is present in plural, they may be different from each other or may form a ring between them (for example, 5-membered ring, 6-membered ring, 7-membered ring, etc.). . X ⁻ is iodine ion, bromine ion, chlorine ion, p-toluenesulfonate ion, perchlorate ion,
Represents an anion such as methylsulfate. However, X does not exist when the general formula (N-II) has a betaine structure.

[0114]

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In the formula, R ₆ represents an alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.) or a substituted alkyl group. Further, R ₆ and R ₈ may form a 6-membered ring or a 5-membered ring. R ₇ is a hydrogen atom, a lower alkyl group (methyl group, ethyl group, propyl group, butyl group,
And a substituted alkyl group or aryl group (phenyl group, alkyl-substituted phenyl group, etc.). R ₆
Examples of the substituent of the substituted alkyl group in R ₇ and R ₇ include a hydroxyl group, an alkoxy group (methoxy group, ethoxy group, etc.), an aryl group (phenyl group, alkyl-substituted phenyl group, etc.) and the like. Specific examples of the substituted alkyl group include, for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, benzyl group,
A 2-phenylethyl group etc. can be mentioned. R ₈
And R ₉ are each independently a lower alkyl group substituted with a hydrogen atom, a lower alkyl group (methyl group, ethyl group, propyl group, etc.), a hydroxyl group, an alkoxy group, an aromatic group (2-hydroxyethyl group, 3- Hydroxypropyl group, 2-methoxyethyl group, 3-ethoxypropyl group,
Benzyl group, 2-phenylethyl group, etc.), alkoxy group (methoxy group, ethoxy group, etc.) or amide group. Further, R ₈ and R ₉ may form a ring such as a 5-membered ring or a 6-membered ring or an aromatic ring.

R ₁₀ is a halogen atom (chlorine atom, bromine atom, etc.), an optionally substituted lower alkyl group, (methyl group, ethyl group, propyl group, 2-hydroxyethyl group,
A 3-hydroxypropyl group, a 2-methoxyethyl group, a benzyl group, etc.), an alkoxy group (a methoxy group, an ethoxy group, etc.) or an amino group which may be substituted with an alkyl group. n4 represents 0, 1 or 2. When there are a plurality of R ₁₀ , they may be different from each other. X ⁻ represents an anion such as an iodine ion, a bromine ion, a chlorine ion, a p-toluenesulfonate ion, a perchlorate ion, and a methylsulfate ion. However, X does not exist when the general formula (N-III) has a betaine structure.

The reduction potential of the pyridinium salt derivatives is -1.
Compounds less base than 60 volts, more preferably -0.80
Use compounds that are less base than bolts.

The value of the reduction potential Ered used here means the potential at which pyridinium salt derivatives are reduced by the electron injection at the cathode in voltammetry.

The value of the reduction potential Ered can be accurately measured by voltammetry. That is, voltammograms of 1 × 10 ⁻³ M to 1 × 10 ⁻⁴ M of pyridinium salt derivatives were measured in acetonitrile containing 0.1 M of tetra-n-butylammonium perchlorate as a supporting electrolyte, and were obtained from this. It was calculated as the half-wave potential. Platinum was used as the working electrode and saturated calomel electrode (S
CE) was used and the measurement was carried out at 25 ° C. More specifically, U.S. Pat. No. 3,501,307 and Dorahai (P.
Delahay), "New Instrumental
Methodes in Electro Chemistry (New I
nstrumental Methods in Ele
(Ctrochemistry) ”(Interscience Publishers)
Blissers), 1954) and the like.

Typical examples of the pyridinium salt derivatives used in the present invention are shown below, but the present invention is not limited thereto.

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These pyridinium salt derivatives are described in "Large Organic Chemistry", Vol. 16 (III), pages 7 and 12 under the supervision of Mitsuo Kotake.
As described on page 9 (1959, Asakura Shoten), it can be synthesized by reacting the corresponding pyridine, quinoline or isoquinoline derivative with an alkyl halide derivative. The specific synthesis method is. A. Grob, E .; R
Env, Helv. Chim. Acta 3
7 , 1672 (1954); E. FIG. Lyle, E .;
F. Perlowski, H, J, Troscani
ec, G.I. G. FIG. Lyle, J. J. Org. Che
m, 20 , 1761 (1955); R. Lambo
rg, R.A. M. Burton, N.M. O. Kaplan, J. Am. Am. Chem, Soc. 79 , 6173
(1957); Ciusa, A .; Buccelli
Author's report, Gazzetta Chimia Itali
ana 88 , 393 (1958) and the like.

The pyridinium salt derivatives used in the present invention are at least one negative-working silver halide emulsion layer constituting the silver halide photographic light-sensitive material or a non-light-sensitive layer composed of other hydrophilic colloid layers, such as a protective layer. It may be contained in a layer, an intermediate layer, an antihalation layer, a filter layer and the like.

The addition amount of the pyridinium salt derivative used in the present invention to the silver halide photographic light-sensitive material is appropriately in the range of 1 × 10 ⁻⁶ to the equimolar amount, and usually 1 × 10 ⁶ per mol of silver halide. ^-4 mol to 0.1 mol is preferably used. Further, the pyridinium salt derivatives used in the present invention can be used alone or in combination.

In order to add the pyridinium salt derivatives used in the present invention to the negative type silver halide emulsion layer or the other non-photosensitive layer, water or a water-miscible organic solvent such as alcohols, ketones, It may be dissolved in an ester or amide and added to a negative silver halide emulsion or a non-photosensitive hydrophilic colloid solution.

The pyridinium salt derivative used in the present invention may be added to the silver halide photographic light-sensitive material at any time during the process for producing the silver halide photographic light-sensitive material. For example, when it is added to a negative type silver halide emulsion, it can be added at any time from the start of chemical ripening to before coating, but it can be added at any time after the end of chemical ripening and immediately before coating. preferable.

Although the mechanism of action of the pyridinium salt derivative in the present invention is not sufficiently clear, the pyridinium salt derivative undergoes a nucleation reaction during the development processing using an alkaline developer to obtain the sensitivity and sensitivity of the silver halide photographic light-sensitive material. It is presumed that it acts as a contrast enhancer that enhances gradation.
Such pyridinium salt derivatives have not been known so far to have extremely high sensitivity and ultra-high contrast effect, which is an unexpected effect.

In the present invention, the developing agent of the general formula (1) according to the present invention and 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl) are used. -4,4-Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol,
2,4-diaminophenol and the like) can be used in combination. In that case, the developing agent for 3-pyrazolidones and aminophenols is usually 1
It is preferably used in an amount of 0.01 to 1.4 mol per liter.

The developer of the present invention may contain a compound represented by the following general formula (S).

General formula (S) Z ¹ —SM ^{1 In the} formula, Z ¹ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ¹ group, a —COOM.
^At least one selected from the group consisting of ^one group (wherein M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonio group Or
It represents those substituted with at least one substituent selected from this group. M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

Further, in the general formula (S), the alkyl group represented by Z ¹ is preferably one having 1 to 30 carbon atoms, particularly straight chain, branched or cyclic alkyl having 2 to 20 carbon atoms. The group may have a substituent in addition to the above substituents. The aromatic group represented by Z ¹ preferably has 6 carbon atoms.
To 32 monocyclic or condensed rings, which may have a substituent in addition to the above substituents. The heterocyclic group represented by Z ¹ is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and contains 1 to 6 heteroatoms in one ring independently selected from nitrogen, oxygen and sulfur. And may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. The ammonio group preferably has 20 or less carbon atoms and the substituent is a substituted or unsubstituted linear, branched, or cyclic alkyl group (eg, methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group). Etc.), a substituted or unsubstituted phenyl group or a naphthyl group. Among the compounds represented by the general formula (S), a compound in which Z ¹ is preferably a heterocyclic group having two or more nitrogen atoms.

Further, among the compounds represented by the general formula (S), more preferred are the compounds represented by the following general formula (Sa).

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In the formula, Z is a group necessary for forming an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (eg, pyrrole, imidazole, pyrazole, pyrimidine, pyridazine, pyrazine, etc.). A compound having at least one -SM ¹ group or a thione group,
And a hydroxyl group, a -COOM ¹ group, a -SO ₃ M ¹ group,
It has at least one substituent selected from the group consisting of a substituted or unsubstituted amino group and a substituted or unsubstituted ammonio group. In the formula, R ¹¹ and R ¹² represent a hydrogen atom, -S
M ¹ group, halogen atom, alkyl group (including those having a substituent), alkoxy group (including those having a substituent), hydroxyl group, —COOM ¹ group, —SO ₃ M
¹ group, alkenyl group (including those having a substituent), amino group (including those having a substituent), carbamoyl group (including those having a substituent), phenyl group (including those having a substituent) And R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5- or 6-membered ring, and is preferably a nitrogen-containing heterocycle. M ¹ is the same as M ¹ defined for the compound represented by formula (S). Preferably, Z is a group forming a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the aforementioned -SM ¹ group or thione group, and the substituent is a halogen atom. (For example, fluorine, chlorine, bromine), lower alkyl groups (including those having a substituent, those having 5 or less carbon atoms such as a methyl group and an ethyl group are preferable), lower alkoxy groups (having a substituent) Including those having 5 or less carbon atoms such as methoxy, ethoxy and butoxy), lower alkenyl groups (including those having a substituent, preferably those having 5 or less carbon atoms), carbamoyl groups, phenyl groups and the like. Can be mentioned. Further, compounds represented by the following general formulas A to F in the general formula (Sa) are particularly preferable.

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In the formula, each of R ₁ , R ₂ , R ₃ and R ₄ is a hydrogen atom, a —SM ₁ group, a halogen atom, a lower alkyl group (including those having a substituent, such as a methyl group and an ethyl group. A group having 5 or less carbon atoms), a lower alkoxy group (including a group having a substituent, a group having 5 or less carbon atoms is preferable), a hydroxy group, -COOM ₂ , -SO ₃ M ₃ group,
A lower alkenyl group (including those having a substituent, preferably a group having 5 or less carbon atoms), an amino group, a carbamoyl group, and a phenyl group, at least one of which is a -SM ₁ group. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. In particular, -SM ₁ substituent other than The hydroxy group, -COOM _2, -SO ₃ M ₃ group, it preferably has a water-soluble group such as an amino group. The amino group represented by R ₁ , R ₂ and R ₃ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compound represented by the general formula (S) as the silver sludge inhibitor are shown below, but the invention is not limited thereto.

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The amount of the compound of the general formula (S) used in the present invention is
It is preferably 10 ^-6 to 10 ^-1 mol, and more preferably 10 ^-5 to 10 ^-2 mol, in 1 liter of the developing solution.

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

In the present invention, the developer contains an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.). ) Is preferably added. As the pH buffering agent, carbonate is preferable, and the amount of addition is preferably 0.5 mol or more and 2.5 mol or less, more preferably 0.75 mol or more and 1.5 mol or less per liter. If necessary, a solubilizing agent (eg, polyethylene glycols, their esters, alkanolamines, etc.), a sensitizer (eg, polyoxyethylene-containing nonionic surfactants, quaternary ammonium compounds, etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, the pH is 8.
It is 5 or more and 10.4 or less.

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

As a special type of development processing, a developing agent is contained in a light-sensitive material, for example, in an emulsion layer or an adjacent layer thereof,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Further, a light-sensitive material containing a developing agent in a light-sensitive material, for example, an emulsion layer or an adjacent layer thereof may be processed with a developer. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8.

As the fixing agent, thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixer contains a water-soluble aluminum salt that acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates capable of softening water. Compounds such as agents may be included.

In the present invention, the ammonium ion concentration in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution.

The ammonium ion concentration is particularly preferably in the range of 0 to 0.05 mol per liter of fixing solution. As the fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

In the present invention, the concentration of acetate ion in the fixing solution is preferably less than 0.33 mol / l. The type of the acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates the acetate ion in the fixing solution. However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used, and particularly sodium salt. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably 0.22 mol or less, and particularly preferably 0.13 mol or less, per 1 l of the fixing solution, whereby the acetic acid gas generation amount can be highly reduced. Most preferably, it is substantially free of acetate ions.

The fixing solution preferably contains thiosulfate. Examples of the thiosulfate include lithium, potassium, sodium and ammonium salts, preferably sodium salt or ammonium salt. The amount of thiosulfate added is 0.1 to 5 mol, more preferably 0.5 to 2.0 mol, and still more preferably 0.7 to 1 mol, per liter of the fixing solution.
1.8 mol. Most preferred is 0.8 to 1.5 moles.

The fixer contains citric acid, tartaric acid, malic acid,
Salts such as succinic acid and optical isomers thereof are included. As salts of citric acid, tartaric acid, malic acid, succinic acid, etc., these lithium salts, potassium salts, sodium salts, ammonium salts, etc., such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, potassium potassium tartaric acid, tartaric acid Sodium potassium and the like may be used. Of these, more preferred are citric acid, isocitric acid, malic acid, succinic acid and salts thereof. Most preferably, malic acid and its salt.

In the present invention, the fixing treatment is followed by washing with water and / or treatment with a stabilizing bath. As a stabilizing bath, the pH of the film is adjusted for the purpose of stabilizing the image (the film surface p after the treatment is adjusted).
Inorganic and organic acids and salts thereof for converting H to 3 to 8 or alkaline agents and salts thereof (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, hydroxide) Sodium, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid,
Malic acid, acetic acid, etc. are used in combination), aldehydes (eg formalin, glyoxal, glutaraldehyde etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc.), anti-bacterial agents. Agents (for example, phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, P-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one,
Dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjusting agent and / or residual color improving agent (for example, mercapto group). A nitrogen-containing heterocyclic compound having as a substituent; specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl -1, 3,
4-triazole, 2-mercaptohypoxanthine, etc.)
Is contained. Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form. In the case of replenishing in solid form, the above-mentioned production method and use method of the solid treatment agent can be used.

In order to reduce the amount of waste liquid, the present invention is processed while supplementing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The developer replenishing amount and the fixer replenishing amount are 50 to 300 ml per 1 m ² . It is preferably 50 to 150 ml per 1 m ² .
The developer replenishing amount and the fixer replenishing amount herein refer to the amount of replenishing liquid. Specifically, it is the replenishing amount of each liquid when replenishing the same liquid as the developing mother liquor and the fixing mother liquor, and each concentrating liquid when replenishing with the developer concentrated liquid and the fixing concentrated liquid diluted with water. And the total amount of water and the total amount of the solid processing agent volume and the water volume when the solid development processing agent and the solid fixing processing agent are replenished with a liquid dissolved in water. And the total amount of the solid processing agent volume and the water volume when the solid fixing processing agent and water are separately replenished. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as or different from the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine. In particular, when the developer replenishment amount is 120 ml or less per 1 m ² , the developer replenisher is preferably a liquid or a solid processing agent different from the developer mother liquor in the tank of the automatic processor, and the mercapto group contained in the developer replenisher is preferable. It is preferable that the amount of the silver sludge inhibitor having the formula (1) is larger than the amount contained in the developing mother liquor, and the amount of the compound represented by the general formula (1) of the present invention or the transition metal complex salt contained in the developing replenisher is in the developing mother liquor. 1.2 to 4 times the included amount
It is preferably doubled. Especially, the fixer replenishment amount is 1
When the amount is 150 ml or less per m ² , the fixing and developing replenisher is preferably different from the fixing mother liquor in the tank of the automatic processor or a solid processing agent, and the amount of thiosulfate contained in the fixing replenisher is fixed. It is preferably larger than the amount contained in the mother liquor.

In the present invention, the developer and the fixing agent, which are solid processing agents, may be dissolved in water.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

In order to shorten the developing time, the present invention provides a total processing time (Dry to Dry) of 10 days from the time when the leading edge of the film is inserted into the automatic developing machine to the time when it comes out of the drying zone when the processing is performed using the automatic developing machine. It is preferably not less than 2 seconds and not more than 50 seconds. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing, stabilization, and drying. This is a time including all the time of the process, that is, a time of Dry to Dry. Total processing time is 1
If the time is less than 0 second, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dr)
y) is 15 to 44 seconds. The development time is preferably 2 seconds or more and 18 seconds or less in order to stably run a large amount of a light-sensitive material of 10 m ² or more.

In the automatic processor, a heat transfer material having a temperature of 60 ° C. or higher (for example, a heat roller at 60 to 130 ° C.) or 150
C. or higher radiating objects (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, and silicon carbide, etc.). A material that emits infrared rays by transmitting heat to a radiator such as ceramics or the like) and having a drying zone is preferably used.

As the heat transfer material having a temperature of 60 ° C. or higher,
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller, and the gear is rotated in the carrying direction by the drive means and the drive transmission means. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

Further, the temperature controller is connected with a thermistor arranged in contact with the outer peripheral surface of the heat roller so that the temperature detected by the thermistor is 60 to 150 ° C, preferably 70 to 130 ° C. In addition, it is preferable to control the halogen heater on / off.

The following examples can be given as examples of the radiation object that emits a radiation temperature of 150 ° C. or higher (preferably 250 ° C. or higher). Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, and lanthanum chromate are directly heated and radiated to control the radiant temperature or heat from a resistance heating element. There is a method of transmitting energy to the radiator and controlling it, but copper,
Stainless steel, nickel, various ceramics, etc.

In the present invention, a heat transfer material having a temperature of 60 ° C. or higher and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

Further, in the present invention, an automatic developing machine having the method and mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regeneration purifying agent and apparatus: JP-A-6-250352, page (3), page "0011" to page (8), page "0058".

(3) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(4) Rinse bath between developing bath and fixing bath: JP-A-4-313749 (18), "0054" to (2)
1) Page "0065".

(5) Water replenishment method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(6) Method of controlling the drying air of the automatic processor by detecting the outside air temperature and humidity, JP-A-1-315745, 496, (2) page, lower right column to 50
1 (7) lower right column and JP-A-2-108051 588
(2) Lower left column of page to 589 (3) Lower left column of page.

(7) Method for recovering silver from fixing waste liquid: JP-A-6-
No. 27623, page (4) “0012” to page (7) “00”
71 ".

Next, the silver halide light-sensitive material applicable to the present invention will be described.

The silver halide composition in the emulsion used in the silver halide light-sensitive material applicable to the present invention is not particularly limited, but in the case of processing with a small replenishment amount or in the case of rapid processing. It is preferable to use a silver halide emulsion having a composition of silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of the silver halide grains of the silver halide light-sensitive material applicable to the present invention is not limited, and may be tabular, spherical, cubic, tetradecahedral, regular octahedral or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

In the silver halide light-sensitive material applicable to the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. A method of maintaining a constant pAg in a liquid phase in which silver halide is formed, as one type of the double jet method;
That is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the silver halide light-sensitive material applicable to the present invention, at least one silver halide emulsion in the silver halide emulsion layer contains tabular grains, and all the emulsion layers in which tabular grains are used. 50% of the total projected area of the particles
The above are preferably tabular grains having an aspect ratio of 2 or more. Particularly, as the proportion of tabular grains increases from 60% to 70%, and more preferably to 80%, more favorable results are obtained.
The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes. 50
Since tabular grains composed of silver chloride of mol% or more have (100) as the main plane, they can be represented by an aspect ratio rather than a scale of aspect ratio, and the ratio is preferably 1.2 to 8.
Further, iodide can be contained in the internal nucleation site in the range of 0.001 to 1 mol%. For tabular grains having a large amount of silver chloride component, the method described in U.S. Pat. No. 5,320,938 can be referred to. The presence of 0.001 mol% or more and less than 10% of high silver iodide sites or the presence of silver nuclei in the silver halide grains is preferable for improving the pressure resistance of the grains. The larger the aspect ratio or the aspect ratio, the flatter the plate. The preferred thickness of the tabular grains is 0.
Although it becomes 01 to 0.5 μm, it can be arbitrarily selected by setting the aspect ratio and the average volume particle diameter. Further, the distribution of the grain size of tabular grains has a coefficient of variation which is often used (100 times the value S / D obtained by dividing the standard deviation S when the projected area is approximated by a circle by the diameter D) of 30% or less, particularly A monodisperse emulsion having a content of 20% or less is preferable. Further, two or more kinds of tabular grains and normal crystal grains can be mixed.

Among these tabular grains, tabular grains having a (100) plane as a principal plane and having a silver chloride content of 50 mol% or more are preferably used. These are described in US Pat.
No. 4,337, No. 5,314,798, No. 5,3
No. 20,958, etc., and the target tabular grain can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. Further, in order to control the photosensitive nuclei, it is possible to provide a transition line on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions. The preparation of the particles can be appropriately selected from an acid method, a neutral method, an ammonia method and the like.
When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5.

In order to control the growth of tabular grains during grain formation, silver halide solvents such as ammonia, thioethers, thiourea compounds and thione compounds can be used. As a thioether compound, 3,6,9,15 described in German Patent 1,147,845,
18,21-hexoxa-12-thiatricosan, 3,
9,15-trioxa-6,12-dithiaheptadecane; 1,17-dioxy-3,9-15-trioxa-
6,12-dithiaheptadecane-4,14-dione;
1,20-dioxy-3,9,12,18-tetroxa-6,15, -dithiaeicosane-4,17-dione;
7,10-Dioxa-4,13-dithiahexadecane-
2,15-dicarboxamide is mentioned. JP 56
-94347, oxathioether compounds described in JP-A-1-121847, JP-A-63-259653,
Examples thereof include cyclic oxathioether compounds described in JP-A No. 63-301939. Especially as thiourea,
Those described in No. 82408 are useful. Specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea; 1,3-dimethylimidazole-2-thione; 1,
3-dimethylimidazole-4-phenyl-2-thione; tetrapropylthiourea and the like.

During physical aging or chemical aging, metal circles such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. Iridium 10 to obtain high illuminance characteristics
Doping in the range ^-9 to 10 ^-3 is often customary in silver halide emulsions. In the present invention, in order to obtain a high-contrast emulsion, it is preferable to dope rhodium, ruthenium, osmium and / or rhenium in the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide.

When the metal compound is added to the particles,
Metals include halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl,
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A No. 2-20.
No. 82, No. 2-20853, No. 2-20854, No. 2-20855, etc., 6-dentate ligands, common sodium salts and potassium salts as alkali complex salts,
There are cesium salts or primary, secondary and tertiary amine salts. It is also possible to form transition metal complex salts in the form of aco complexes. Examples of these include, for example, K ₂ [RuCl ₆ ],
(NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO) Cl
₄ (SCN)], K ₂ [RuCl ₅ (H ₂ O)] and the like. The part of Ru is Rh, Os, Re, I
It can be represented by being replaced with r, Pd, and Pt.

Rhodium, ruthenium, osmium and /
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion.

It is often the case that better results are obtained when more shells are present. In addition, instead of being localized in a discontinuous layer configuration, a method of increasing the abundance as the particles are continuously outside the particles may be used. The addition amount can be appropriately selected within the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
search Disclosure, RD) 17
No. 6, 17643, pages 22 to 23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499 and JP-A-50-7132.
The compounds described in JP-A No. 5 and JP-A-60-150046 can be preferably used.

As the tellurium sensitizer, known tellurium sensitizers can be used. For example, US Pat.
499, 3,772,031, 3,320,0
The compounds described in No. 69 and the like can be preferably used.

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

As reduction sensitizers, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

The sensitizing effect can be further enhanced by adding these sensitizers in the form of fine particles dispersed therein. Also, AgI
When particles are finely dispersed and added during chemical sensitization, AgI is formed on the surface of the particles, and the effect of dye sensitization can be enhanced. When forming tabular grains of AgI, the contribution of the transition line portion ranging from 0 to 1000 is often utilized.

Selenium sensitizers include a wide variety of selenium compounds.

For example, in this regard, US Pat.
74,944, 1,602,592, 1,62
3,499, JP-A-60-150046, JP-A-4
-25832, 4-109240, 4-147.
No. 250, etc.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-
Heptafluoropropylcarbonylselenourea, N,
N, N′-trimethyl-N′-4-nitrophenylcarbonylselenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.) , Selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosphate, diphenyltetrafluorophenylselenophosphate, etc.) ),
Selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

Specific examples of the technique for using these selenium sensitizers are described in US Pat. Nos. 1,574,944 and 1,602,5.
No. 92, No. 1,623,499, No. 3,297,44
No. 6, No. 3,297,447, No. 3,320,069
No. 3, ibid. 3,408,196, ibid. 3,408,197
Issue No. 3,442,653 Issue 3,420,670
No. 3,591,385.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but is generally 10 ^-8 to 10 ^-3 per mol of silver halide.
Use about moles. The addition method is, depending on the properties of the selenium compound used, a method of adding it by dissolving it in water or an organic solvent such as methanol and ethanol alone or in a mixed solvent, or by adding it in advance with a gelatin solution. Alternatively, the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used. Further, it can be used by making a solid dispersion having a particle diameter of 0.01 to 500 μm. The solid dispersion method can be produced according to the solid dispersion method of the dye or pigment. The temperature of chemical ripening using the selenium sensitizer in the present invention is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C. or higher and 80 ° C. or lower. The pH is preferably in the range of 4 to 9, and the pAg is preferably in the range of 5 to 10 adjusted with a water-soluble halide such as potassium bromide or sodium chloride or silver nitrate.

Tellurium compounds can be used in addition to the selenium compounds. Tellurium compounds are Se of selenium compounds.
Can be represented by substituting a Te atom. For example, N, N-dimethyl tellurourea, N, N, N'-triethyl tellurourea, N, N, N'-trimethyl-N '
-Heptafluoro tellurourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonyl tellurourea,
Diphenyl tetrafluorophenyl tellurophosphate,
Diphenyl pentafluorophenyl tellurophosphate,
Examples thereof include triphenylphosphine selenide.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus And a quinoline nucleus. These nuclei may be substituted on carbon atoms. As a core having a ketomethylene structure in the merocyanine dye or composite merocyanine dye,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- to 6-membered heterocyclic ring such as a 2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. Specifically, those described in RD 176, 17643 (December, 1978), pages 2-3, US Pat. Nos. 4,425,425 and 4,425,426 can be used. The sensitizing dye is described in US Pat. No. 3,485,634.
The dissolution may be carried out using ultrasonic vibration described in the above item. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention and adding it to an emulsion, US Pat.
981, No. 3,585,195, No. 3,469,9
87, 3,425,835, 3,342,60
5, British Patents 1,271,329, 1,038,
029, 1,121,174, U.S. Pat. No. 3,66.
Nos. 0,101 and 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in RD 176, 17643, issued December 1978, page 23, IV, section J.

The light-sensitive material applicable to the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. it can. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As the gelatin, other than lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

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

It is preferable to contain a hydrophilic polymer in at least one constituent layer. Preferred hydrophilic polymers include starch, glucose, dextrin, dextran, cyclodextrin, sucrose, maltose, xanthan gum, carrageenan, and the like. The molecular weight of the hydrophilic polymer can be appropriately selected from 600 to 1,000,000. The lower the molecular weight is, the better to elute into the processing solution quickly during the processing, but if it is too low, the film strength of the film is deteriorated. When a hydrophilic polymer is used, the scratch resistance of the film deteriorates, so inorganic colloidal silica, colloidal tin, colloidal zinc,
It is preferable to add colloidal titanium, colloidal yttrium, colloidal praseodymium, neodymium, zeolite, apatite and the like. As a zeolite,
Analcite, erionite, mordenite, chabazite, gmelinite, levinite, and synthetic zeolites such as zeolites A, X, Y, and L are listed.
Examples of apatite include hydroxyapatite, fluorospatite, and chlorapatite. The preferable addition amount is 1 to 200% by weight with respect to the hydrophilic binder. By treating the above inorganic compound with a silane coupling agent, the inorganic compound hardly aggregates even when added to an emulsion, and can stabilize a coating solution.
Further, cracking due to the inorganic compound can be prevented. As silane coupling agents, triethoxysilanovinyl, trimethoxysilanovinyl, trimethoxypropyl methacrylate, trimethoxysilanopropylglycidyl, 1-mercapto-3-triethoxysilanopropane, 1-amino-3-triethoxysilanopropane, Triethoxysilanophenyl, triethoxymethylsilane and the like. The properties of the silane coupling agent can be improved by performing a high temperature treatment together with the above-mentioned inorganic compound, compared to the simple mixing. The mixing ratio is 1:
It is better to select in the range of 100 to 100: 1.

It is preferable to have at least one hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer and at least one hydrophobic polymer layer on the outside thereof.
Here, the hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer includes a so-called back layer. In the present invention, a structure having at least one hydrophobic polymer layer outside the back layer is preferable.

The hydrophobic polymer layer in the present invention is a layer containing a hydrophobic polymer as a binder. Specific examples of the binder of the polymer layer, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin,
Epoxy resins, fluororesins such as tetrafluoroethylene and polyvinylidene fluoride, butadiene rubber, chloroprene rubber, rubbers such as natural rubber, acrylic acid or methacrylic acid esters such as polymethylmethacrylate and polyethylacrylate, polyethylene phthalate, etc. Examples thereof include polyester resins, polyamide resins such as nylon 6, nylon 66, cellulose resins such as cellulose triacetate, water-insoluble polymers such as silicone resins, and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. Particularly preferred binders include alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid copolymers (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymer, styrene-butadiene-acrylic acid copolymer (acrylic acid is Styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride -Acrylonitrile-methyl methacrylate-ethyl acrylate-acrylic acid copolymer (5 mol% or less of acrylic acid), ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer and the like. These may be used alone or in combination of two or more.

The hydrophobic polymer layer in the present invention may include a matting agent, a surfactant, a dye, a slip agent, a cross-linking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica for photographic use, if necessary. Additives may be added. These additives are also described in RD Volume 176, Item 17646 (1978).
You can refer to the description etc.

The hydrophobic polymer layer in the invention may be one layer or two or more layers.

The thickness of the polymer layer is not particularly limited. However, if the thickness of the hydrophobic polymer layer is too small,
The water resistance of the hydrophobic polymer layer becomes insufficient, and the back layer becomes swelled in the treatment liquid, which is inappropriate. Conversely, if the thickness of the hydrophobic polymer layer is too large, the water vapor permeability of the polymer layer becomes insufficient, and the moisture absorption and desorption of the hydrophilic colloid layer of the back layer is inhibited, resulting in poor curl. Of course, the thickness of the hydrophobic polymer layer also depends on the physical properties of the binder used. Therefore, the thickness of the polymer layer needs to be determined in consideration of both. The preferable thickness of the hydrophobic polymer layer depends on the binder species of the hydrophobic polymer layer, but is 0.05 to 10 μm, more preferably 0.1 to 10 μm.
The range is 5 μm. When the hydrophobic polymer layer of the present invention comprises two or more layers, the sum of the thicknesses of all the hydrophobic polymer layers is defined as the thickness of the hydrophobic polymer layer of the silver halide photographic light-sensitive material of the present invention.

The method for applying the above-mentioned hydrophobic polymer layer is not particularly limited. After coating and drying the back layer, a polymer layer may be coated on the back layer and then dried, or the back layer and the hydrophobic polymer layer may be simultaneously coated and then dried. The hydrophobic polymer layer may be applied in a solvent system by dissolving in a solvent of a binder of the polymer layer, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

On the surface of the black and white silver halide photographic light-sensitive material opposite to the emulsion layer, it is preferable to provide an adhesive layer / antistatic layer / back layer containing a hydrophilic colloid / hydrophobic polymer layer on a support. . Further, a protective layer may be provided thereon. As the adhesive layer, a vinylidene chloride copolymer or a styrene-glycidyl acrylate copolymer is applied to a corona-discharged support in a thickness of 0.1 to 1 μm, and then an indium or phosphorus-doped average particle size of 0.01 is applied. It can be obtained by coating with a gelatin layer containing fine particles of tin oxide and vanadium pentoxide of ˜1 μm. Further, a styrene sulfonic acid and maleic acid copolymer can be formed by forming a film with the aziridine or carbonyl active type crosslinking agent described above. A dye back layer may be provided on these antistatic layers. These layers should contain inorganic fillers such as colloidal silica for dimensional stability, silica or methyl methacrylate matting agent for adhesion prevention, silicon-based slip agent or release agent for transportability control, etc. Can be. The back layer may contain a backing dye, and as the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can be fixed as fine particles. The concentration for preventing halation is 0.1 to 2 at each photosensitive wavelength.
Preferably, the concentration is up to zero.

An inorganic or organic hardener is added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer as a crosslinking agent for the hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-
Methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) ) Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activating type hardener and the like can be used alone or in combination. These hardeners are RD 176 vol 176
43 (issued December 1978), page 26, paragraphs AC.

Of these, carboxyl group-activating type hardeners are preferable, and they are disclosed in JP-A-5-289219, pp. 3-5.
The compounds represented by the general formulas (1) to (7) described on page are preferable, and specific examples thereof include, for example, pages 6 to 1 of the same specification.
H-1 to H-39 described on page 4 can be mentioned. As the hardener used in the silver halide photographic light-sensitive material applicable to the present invention, the following general formula

Examples thereof include compounds represented by [9].

[0238]

Embedded image

General formula

In the compound represented by [9],
R ₁₂ and R ₁₃ have a linear, branched or cyclic carbon number of 1 to
Examples thereof include 20 alkyl groups (eg, methyl group, ethyl group, butyl group, cyclohexyl group, 2-ethylhexyl group, dodecyl group) and aryl groups having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group). Also R ₁₂ and R ₁₃
May have a substituent.
General formula [1] to general formula [6] described in -289219
Examples of the substituents of R _{1 to} R ₁₁
It is also preferable that R ₁₂ and R ₁₃ combine to form a ring together with the nitrogen atom, and a particularly preferable example is the case of forming a morpholine ring or a pyrrolidine ring. R ₁₄ represents a hydrogen atom or a substituent, and examples of the substituent include JP-A-5-2892.
R _{1 to} R ₁₁ of the general formula [1] to general formula [6] described in No. 19
The substituents mentioned above can be mentioned, but a hydrogen atom is particularly preferable.

L represents a single bond, an alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group), an arylene group having 6 to 20 carbon atoms (eg, phenylene group), and It represents a divalent group such as a divalent group (for example, a baraxylene group), an acylamino group (for example, —NHCOCH ₂ — group), a sulfonamide group (for example, —NHSO ₂ CH ₂ — group) and the like obtained in combination. Preferred are a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group.

X ₃ is a single bond or --O--, --N
(R ₁₅ )-, wherein R ₁₅ is a hydrogen atom or has 1 to 1 carbon atoms.
20 alkyl group (for example, methyl group, ethyl group, benzyl group, etc.), C 6-20 aryl group (for example, phenyl group), C 1-20 alkoxy group (for example,
Methoxy group), and a hydrogen atom is particularly preferable. Specific examples of preferred hardeners are given below.

[0242]

Embedded image

Other preferable compounds as the hardener include compounds (1) to (17) described in Japanese Patent Application No. 6-144823, pages 11 to 13.

The light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer have various known substances for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. A surfactant may be used.

In each layer, in addition to gelatin, dextrins,
The degree of swelling can be adjusted by introducing a hydrophilic polymer such as starch or glucose or a hydrophobic latex. The degree of swelling is generally 120 to 200. For drying each layer, the temperature and time are adjusted according to the evaporation rate of water.
A temperature of 25 ° C. to 200 ° C. and a time of 0.1 second to 200 seconds are generally applied. The degree of swelling can be measured by immersing in water and measuring with a microscope, or by a swelling degree meter. As the degree of swelling, dry film thickness = Ld (23 ° C., 50
% Relative humidity (film thickness after conditioning for 24 hours) 23 ° C
The ratio of the swollen thickness Lw in water (Lw / Ld) is 10
A value multiplied by 0 can be used as an index.

The surface tension and the wetting index can be determined with reference to JIS.

The film surface pH on the silver halide photographic emulsion layer side is:
It is preferably 4.5 or more and 5.8 or less. Membrane pH
Is the pH measured after coating and drying, and the measurement is carried out by dropping 1 ml of pure water per 1 cm ^{2 of the} measured portion with a pH meter. When lowering the pH, use acids such as citric acid, oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and carbonic acid.
When raising, sodium hydroxide, potassium hydroxide,
Alkaline agents such as sodium carbonate, sodium hydrogen carbonate, sodium acetate and the like can be used. The same method can be applied when adjusting the pH when using a photographic additive.

Various other additives are used in the silver halide photographic light-sensitive material applicable to the present invention. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

The support used in the silver halide photographic light-sensitive material applicable to the present invention may be either transparent or non-transparent, but a transparent plastic support is preferable. As the plastic support, a support made of a polyethylene compound (eg polyethylene terephthalate, polyethylene naphthalate etc.), a triacetate compound (eg triacetate cellulose etc.), a polystyrene compound etc. is used. Among these, a support (hereinafter abbreviated as SPS) formed of a stretched film made of a styrene polymer having a syndiotactic structure or a composition containing the styrene polymer is particularly preferable.

The SPS refers to a homopolymer whose constituent unit is composed of SPS units having syndiotactic stereoregularity, but in a small amount, for example, 20 mol% or less, preferably 10 mol% or less, more preferably Also includes SPS modified with 5 mol% or less of the second component. As the second component, for example, ethylene, propylene,
Examples thereof include olefin monomers such as butene and hexene, diene monomers such as butadiene and isoprene, cyclic olefin monomers, cyclic diene monomers, polar vinyl monomers such as methyl methacrylate, maleic anhydride, and acrylonitrile. In general, it is produced by polymerizing styrene or a derivative thereof under an appropriate reaction condition using an organometallic catalyst. 75 is a racemic diad.
% Or more, preferably 80% or more, or a racemic pentad having a stereoregularity of 30% or more, preferably 50% or more. In this case, a general plastic plasticizer can be added as the second component within a range that does not degrade the flexural modulus, and this is performed to obtain an appropriate flexural modulus.

SPS can be synthesized by polymerizing styrene or a derivative thereof at a suitable reaction temperature in the presence of a catalyst of a condensation product of a titanium compound and trialkylaluminum.

These are described in JP-A-62-187708,
The methods described in JP-A-1-46912 and JP-A-1-178505 can be referred to. The polymerization degree of SPS is not particularly limited, but those having 10,000 to 5,000,000 are preferably used. In order to increase the flexural modulus of the SPS, it is necessary to select optimal stretching conditions. 30 ° C. ± 25 ° C. from the glass transition point of the unstretched film, ie, 1
At 20 ° C. ± 25 ° C., the film is first stretched longitudinally 3.3 ± 0.3 times. Next, it is stretched transversely 3.6 ± 0.6 times under the same temperature conditions. Heat treatment after stretching is performed at 230 ± 18 ° C. Good results are obtained when the heat treatment is performed not only in the first stage but also in the second stage. Thus, an SPS film having a flexural modulus of 350 kg / m ² or more is manufactured.

A film having such a high flexural modulus is
It is difficult to apply the photographic layer as it is and adhere it firmly. There are many patents and literature on how to do this,
It can be referred to because it is described on pages 3 to 4 of JP-A-3-54551.

For example, regarding the surface treatment, it is described that a corona discharge treatment or an undercoat layer is further applied. Examples of the undercoat layer include vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

Further, in order to improve the curl and curl of the support, it is preferable to carry out heat treatment after film formation. Most preferred is after film formation and after emulsion coating, but it may be after emulsion coating. The heat treatment condition is preferably 45 ° C. or higher and the glass transition temperature or lower for 1 second to 10 days. From the point of productivity 1
It is preferably within the time.

The compounds described below are preferably contained in the silver halide photographic light-sensitive material applicable to the present invention.

(1) Solid Dispersion Fine Particles of Dye JP-A-7-5629, page (3) [0017] to (16)
Compounds described on page [0042] (2) Compounds having an acid group JP-A-62-237445, 292 (8), page lower left column 1
Compounds described in lines 1 to 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036] to
(17) Compound described on page [0062] (4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (1)
3) Compounds described on page [0040], JP-A-6-1947
No. 71 (11) page [0042] to (22) page [009]
4] The compound described in JP-A-6-242533, page (2) [0015] to
(8) Compound described on page [0034], JP-A-6-337
No. 492, page (3) [0012] to page (34) [005
6], compounds described in JP-A-6-337494, page (4), pages [0013] to (14), [0039] (5) Supersensitizer, JP-A-6-347938, page (3), [0011] ] ~ (1
6) Compound described on page [0066] (6) Redox compound JP-A-4-245243, 235 (7) to 250 (2)
2) Compounds described on page Regarding the above-mentioned additives and other known additives, for example, RD17643 (December 1978), the same No. 1
8716 (November 1979) and the same No. 30811
9 (December 1989). The types of compounds shown in these three RDs and the places where they are described are shown in the following table.

[0259]

[Table 1]

Although various photographic additives may be used by dissolving them in an aqueous solution or an organic solvent, when they are poorly soluble in water, they are made into a fine crystalline state and dispersed in water, gelatin, a hydrophilic or hydrophobic polymer. Can be used. A dye, a dye, a desensitizing dye, a hydrazine, a redox compound, an antifoggant, an ultraviolet absorber and the like can be dispersed by a known disperser. Specifically, ball mill, sand mill,
Examples include a colloid mill, an ultrasonic disperser, and a high-speed impeller disperser. These dispersed photographic additives are 100
Fine particles having an average particle size of less than or equal to μm are usually used with an average particle diameter of 0.02 to 10 μm. As a dispersion method, a method of mechanically stirring at high speed (JP-A-58-58)
No. 105141), a method in which the organic solvent is removed by heating and dissolving it in an organic solvent and dispersing it while adding the gelatin containing a surfactant or antifoaming agent and the hydrophilic polymer described above (JP-A-44-44). No. 22948), dissolved in an acid such as citric acid, acetic acid, sulfuric acid, hydrochloric acid, malic acid or the like to have a pH of 4.5.
To 7.5 in a polymer (Japanese Patent Application Laid-Open No. 50-80119), or by dissolving in an alkali such as sodium hydroxide, sodium hydrogen carbonate or sodium carbonate to obtain p.
A method in which crystals are precipitated and dispersed in a polymer such as gelatin having an H4.5 to 7.5 (JP-A-2-15252) can be applied. For example, hydrazine, which is difficult to dissolve in water, can be dissolved by referring to JP-A-2-3033,
This method can be applied to other additives. Further, a dye having a carboxyl, a sensitizing dye, an inhibitor and the like can increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxyl group. That is, it is preferable to form a hardly soluble salt by adding 200 to 4000 ppm of a calcium ion, a magnesium ion or the like to the hydrophilic colloid layer. The use of other salts is not limited as long as a hardly soluble salt can be formed. The method for dispersing fine particles of a photographic additive is a sensitizer, a dye inhibitor, an accelerator,
The application to a contrast-increasing agent, a contrast-increasing aid, etc. can be arbitrarily made according to its chemical and physical properties.

For simultaneously coating a plurality of constituent layers of 2 to 10 layers at a high speed of 30 to 1000 m / min, the known methods described in US Pat. Nos. 3,636,374 and 3,508,947 are known. Slide hopper or curtain coating can be used. In order to reduce unevenness during coating, it is preferable to lower the surface tension of the coating solution or to use the above-mentioned hydrophilic polymer which can impart a thixotropic property in which the viscosity is reduced by a shearing force.

The silver halide photographic light-sensitive material applicable to the present invention may be provided with a crossover cut layer, an antistatic layer, an antihalation layer and a back coat layer.

A known method is used as a method for packaging the silver halide photographic light-sensitive material applicable to the present invention.

Since the silver halide photographic light-sensitive material is vulnerable to heat and humidity, it is preferable to avoid storing it under severe conditions. Generally, it is better to store at 5 ° C to 30 ° C.
The humidity should be between 35% and 60% relative humidity. It is common practice to package in polyethylene of 1 to 2000 μm to protect from humidity. Polyethylene can suppress the permeation of water by improving the regularity of crystals by using a metallocene catalyst. Moreover, the surface of polyethylene is 0.1-1000μ.
Moisture permeation can be suppressed by silica vapor deposition coating with a thickness of m.

[0265]

The present invention will be specifically described below with reference to examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

(Preparation of Support) (SPS Synthesis) 1 part of styrene was added to 200 parts by weight of toluene.
The reaction was carried out at 96 ° C. for 8 hours using 00 parts by weight, 56 g of triisobutylaluminum and 234 g of pentamethylcyclopentadienyltitanium trimethoxide. After decomposing and removing the catalyst with a methanol solution of sodium hydroxide,
After washing three times with methanol, the target compound (SPS)
4 parts by weight were obtained.

(Preparation of SPS Film) Obtained SPS
Was melt-extruded from a T-die at 330 ° C. into a film and quenched and solidified on a cooling drum to obtain an uncentrifuged film. At this time, the take-up speed of the cooling drum is set in two stages, and the thickness is 1370 μm, 1265 μm and 1054 μm.
The unstretched film of 1. was preheated at 135 ° C and longitudinally stretched (3.1
After that, the film is transversely stretched (3.4 times) at 130 ° C and further 2
Heat fixation was performed at 50 ° C. As a result, a biaxially stretched film having a bending elastic modulus of 450 kg / mm ² and a thickness of 100 μm was obtained as a support.

(Undercoating of SPS Film) After vapor-depositing silica on the above SPS film, an undercoating layer containing styrene-glycidyl acrylate and tin oxide fine particles and subjected to an antistatic treatment was formed.

Example 1 << hydrazine system >> (Preparation of silver halide emulsion A) An average thickness of silver chloride 70 mol% and a balance of silver bromide of 0.05 using a simultaneous mixing method.
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The obtained emulsion was silver / chloroiodobromide (90 mol% of silver chloride) having a core / shell type monodisperse (coefficient of variation: 10%) having a (100) plane as a main plane having an average thickness of 0.10 μm and an average diameter of 0.25 μm. , 0.2 mol% of silver iodobromide, the remainder being silver bromide). Then, the modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139-2)
The salt was desalted using Exemplified Compound G-8) on page 87 (3). The EAg after desalting was 190 mv at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene (HMT) was added to the obtained emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. Then, the pH is adjusted to 5.6 and EAg is 123 mv, 2 × 10 ^-5 mol of chloroauric acid is added, and then 3 × 10 ^-6 mol of inorganic sulfur is added, and chemical aging is performed at a temperature of 60 ° C. until maximum sensitivity is obtained. It was After the ripening, 2 × 10 ⁻³ mol of HMT, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole (FMT) and gelatin were added per mol of silver.

(Preparation of Silver Halide Emulsion B) 60 mol% of silver chloride, 2.5 mol% of silver iodide, the rest of which is silver bromide, and has an average thickness of 0.05 μm and an average diameter of 0.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. %, The rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Then, JP-A-2-28013
No. 9 described in Japanese Unexamined Patent Publication (Kokai) No. 2-2 (the modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl).
Desalting was carried out using the exemplified compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 180 mv at 50 ° C.

HMT was added to the resulting emulsion at 1 per mol of silver.
× 10 ^-3 mol per mol further by addition of potassium bromide and citric acid pH 5.6, was adjusted to EAg123mv, N after chloroauric acid 2 × 10 ^-5 mol was added, N, N'-trimethyl - Add N'-heptafluoroselenourea to 3 × 10 ^-5
Chemical addition was carried out at a temperature of 60 ° C. until the maximum sensitivity was obtained. After completion of ripening, HMT is 2 × 10 per mol of silver.
^-3 mol, 3 x 10 ^-4 mol FMT and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for He-Ne laser light source) On one undercoat layer of the above-mentioned support, a gelatin undercoat layer of the following Formulation 1 was used in which the amount of gelatin was 0. .5g / m at ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon,
The amount of gelatin was 0.5 g / m ^2, and the coating solution of the following formulation 3 was used as an intermediate protective layer on the upper layer thereof so that the amount of gelatin was 0.3 g / m ² and the formulation 4 was further applied on the upper layer thereof. The silver halide emulsion layer 2 had a silver content of 1.4 g / m ² and a gelatin content of 0.4 g / m ^2, and the coating solution of the following formulation 5 had a gelatin content of 0.6 g / m ^2. Simultaneous multilayer coating was performed. On the other side of the undercoat layer, a backing layer of the following formulation 6 was formed so that the amount of gelatin was 0.6 g / m ^2, and a hydrophobic polymer layer of the following formulation 7 was formed on the backing layer, and the following formulation was also formed on the hydrophobic polymer layer. A sample was obtained by simultaneously coating the backing protective layer of No. 8 with the emulsion layer side so that the amount of gelatin was 0.4 g / m ² .

(Formulation 1 Composition of gelatin undercoat layer) Gelatin 0.5 g / m ² Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² (Formulation 2 Silver halide emulsion layer 1 composition) Silver halide emulsion A Dye AD so that the amount of silver becomes 1.5 g / m ² . -8 solid dispersed fine particles (average particle size 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² Hydrazine derivative Exemplified H-7 20 mg / m ² redox compound R-1 20 mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² (formulation 3 intermediate layer composition) gelatin 0.3 g / m ² S-1 2 mg / m ² (formulation 4 silver halide emulsion layer 2 composition) silver halide emulsion B so that the amount of silver is 1.4 g / m ² sensitizing dye d-1 3 mg / m ² sensitizing dye d -2 3 mg / m ² hydrazine derivative illustrative H-20 20mg / m ² nucleation accelerator exemplified Nb-12 40mg / m ² redox compound ^R-2 20mg / m 2 2- mercapto-6-hydroxy-purine 5 mg / m ² EDTA 20 mg / m ² latex polymer ^{f 0.5g / m 2 S-1} 1.7mg / m 2 ( formulation 5 emulsion protective layer composition) solid dispersion of gelatin 0.6 g / m ² dye AD-5 (average Diameter ^{0.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² nucleation accelerator Exemplified Na-3 40mg / m ² 1,3- Vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener: K-2 30 mg / m ² (formulation 6 backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² (formulation 7 hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener g 6 mg / m ² (formulation 8 Kkingu protective layer) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - di - (2-ethylhexyl) - sulfosuccinate 10 mg / m ² Surfactant h 1 mg / M ² Dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener: K-2 20 mg / m ²

[0275]

Embedded image

[0276]

Embedded image

[0277]

Embedded image

The surface resistivity of the backing side after coating and drying was 6 × 10 ^{11 under} the conditions of 23 ° C. and 20% RH, the film surface pH of the emulsion side surface was 5.5, and the swelling degree was 175. .

The composition of the developer is shown below, and the weight (g) is shown unless otherwise specified.

(Developer composition / min. 1 liter of working solution) Pure water 400 ml Potassium carbonate 155 Hydroquinone 16 Dimezone S 1.1 DTPA · 5Na (40 wt%) 1.45 5-Methylbenzotriazole 0.27 FMT 0.03 8- Mercaptoadenine 0.06 Sodium sulfite 31.52 Potassium sulfite 155 Diethylene glycol 50 Sodium erythorbate 38 Diethylaminopropanediol 25 Isoelite P (Saltwater Port salt) 20 Redox compound Amount shown in Table 1 KOH (55% aqueous solution) and pure water are used. To 500 ml (pH 10.45). When used, 500 ml of pure water is mixed and used.

(Fixer Composition) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 Boric acid 9.8 Sodium acetate trihydrate 34 Acetic acid (90% aqueous solution) 14.5 Tartaric acid 3.0 Aluminum sulfate (27% aqueous solution) ) 25 ml The pH of the working solution was 4.9.

Water and sulfuric acid were added to make up to 500 ml, and the pH was adjusted to pH 4.9 at the time of use. At the time of use, 500 ml of water was added to make 1 liter of the developing solution.

[0283] (Evaluation of Large Spot Removability) The light-sensitive material produced as described above was exposed by SG-747RU manufactured by Dainippon Screen Co., Ltd. with halftone dots of a random pattern of 16 μm, and then an automatic processor LD- manufactured by Dainippon Screen Co., Ltd. The treatment was performed at 220 QT using the above treatment solution under the following treatment conditions. The large dot skipping property was evaluated by measuring the dot percentage at the time of 97% dot output at the exposure amount at which 50% dot output was reproduced 50%.

The evaluation results are shown in Table 2 below.

[0285]

[Table 2]

As is clear from these results, when the processing agent of the present invention in which ascorbic acid and its derivative and redox compound are used in combination as the developing agent is used as the developing solution, the reproducible% at 97% halftone dot output is It remains in the 97% range, and it can be seen that the large dots are missing, that is, the dot reproducibility is good.

Example 2 <Pyridinium salt compound system> (Preparation of silver halide emulsion A) Mixing an aqueous solution of silver nitrate, NaCl and KBr so that the silver halide composition is 80 mol% of silver chloride and 20 mol% of silver bromide. The aqueous solution was mixed by the controlled double jet method to grow silver halide grains. At this time, the mixture was 36 ° C., pAg 7.8, pH 3.
Performed under the conditions of 0, K ₃ RuCl ₆ was per mole silver 8 × 10 ^-8 mol of K ₂ IrCl ₆ was added 3 × 10 ^-7 mol per mol of silver in the grain formation. After that, desalting was performed with modified gelatin treated with phenylisocyanate, and ossein gelatin was added and redispersed. The obtained emulsion was cubic grains having an average grain size of 0.18 μm and a coefficient of variation of 10%. To the emulsion thus obtained, 1 × 10 ⁻³ mol of HMT was added per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5.6 and EAg of 123 mv.
And after adding 2 × 10 ⁻⁵ mol of chloroauric acid,
2 × 10 ⁻⁶ mol of N, N, N′-trimethyl-N′-heptafluoroselenourea was added and chemical ripening was performed at a temperature of 60 ° C. until maximum sensitivity was obtained. HMT silver 1 after aging
3 × 10 ⁻³ mol was added per mol.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for He-Ne laser light source) The above SP
On one subbing layer of the S support, a gelatin subbing layer of the following Formulation 1 was added so that the gelatin amount was 1.0 g / m ² , and a silver halide emulsion layer of the Prescription 2 was added in a silver amount. 3.5 g / m
^2. Simultaneous multilayer coating was performed so that the amount of gelatin was 1.5 g / m ² and the coating solution of the following formulation 3 was 0.6 g / m ² . On the other side of the undercoat layer, a backing layer having the following formula 4 was added so that the amount of gelatin was 2.0 g / m ^2, and a backing protective layer having the following formula 5 was added to give a gelatin amount of 1.0 g / m ^2. A sample was obtained by simultaneous multi-layer coating with the emulsion layer side so as to obtain m ² .

(Formulation 1 Composition of gelatin undercoat layer) Gelatin 1.0 g / m ² FMT 1.0 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 0.4 mg / m ² (Formulation 2 silver halide emulsion) Layer composition) Silver halide emulsion A Silver amount 3.5 g / m ² Sensitizing dye d-1 3 mg / m ² Sensitizing dye d-2 3 mg / m ² Pyridinium salt derivative Exemplified compound N-1 52.5 mg / m ² Compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² styrene - hydrophilic polymer maleic acid copolymer (thickener) 15 mg / m ² (formulation 3 emulsion protective layer composition) gelatin ^{0.6g / m 2 S-1 12mg} / m 2 matting agent: average particle size of 3. μm monodisperse silica 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05μm) 20mg / m ² Hardener j 30 mg / M ² (formulation 4 backing layer composition) S-1 5 mg / m ² gelatin 2.0 g / m ² latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² polystyrene sulfonic acid Sodium 20 mg / m ² Compound i 100 mg / m ² (Formulation 5 backing protective layer) Gelatin 1.0 g / m ² Matting agent: Monodisperse polymethylmethacrylate 50 mg / m ² sodium-di- (2-ethylhexyl) having an average particle size of 5 μm ) - sulfosuccinate 10 mg / m ² surfactant h 1 mg / m ² dye ^{k 20mg / m 2 H- (OCH} 2 Except that the pH of the developing solution used in _{H 2) 68 -OH 50mg / m} 2 hardener g 20 mg / m ² Example 1 to 10.00 in the same manner, developing, fixing was carried out large-point loss of An evaluation was made.

The evaluation results are shown in Table 3 below.

[0291]

[Table 3]

From this result, as in Example 1, by using the processing agent of the present invention in which ascorbic acid and its derivative and the redox compound were used in combination with the developing agent as a developing solution, a reproduced network at 97% halftone dot output was obtained. % Is maintained in the 97% range, and it can be seen that the large dot penetration property, that is, the dot reproducibility is good.

Example 3 A running experiment was carried out by the method described below, based on the light-sensitive material used in Example 1 (the species of the redox compound, the addition amount was changed), the processing solution, the automatic processor and the processing conditions. went. Processing was carried out for 10 days at 100 sheets (large size) with the developer replenishment amount shown in Table 3. The treatment was carried out by alternately using the explosive film and the unexposed film, 50 sheets each per day, and 500 sheets each for 10 days. By the same method as in Example 1, the large-point dropout property before the start of running (at the time of a new solution) and after the end of running was evaluated.

The evaluation results are shown in Table 4 below.

[0295]

[Table 4]

As is clear from these results, the replenishment amount of the processing solution of 50 to 300 ml per 1 m ^{2 of the} light-sensitive material is particularly excellent in the large dot escape after the end of running,
It can be seen that the running performance is excellent even if the replenishment amount is small, such as there is not much difference from before the start of running (when using new solution).

[0297]

INDUSTRIAL APPLICABILITY According to the present invention, even when a processing agent for a silver halide photographic light-sensitive material using ascorbic acid and its derivative, which is environmentally friendly and highly safe, is used, a large number of dot penetration, that is, halftone dot reproducibility is obtained. Has a remarkably excellent effect of providing a good processing method of a silver halide photographic light-sensitive material. Further, the large-point drop-out property after the end of running is good, and there is not much difference from that before the start of running, and therefore the running property is excellent even if the replenishment amount is small.

Claims (5)

[Claims] 1. A processing agent for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one surface of a support, which does not substantially contain hydroquinone and has the following general formula (1): ), And a redox compound which releases a development inhibitor when oxidized, and a processing agent for silver halide photographic light-sensitive materials. Embedded image [In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted (alkyl group, amino group, alkoxy group, alkylthio group)
And R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ] 2. The processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein at least one layer on the side having the silver halide emulsion layer contains at least one hydrazine derivative. 3. The processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein at least one layer having the silver halide emulsion layer contains at least one pyridinium salt compound. 4. A method of processing a silver halide photographic light-sensitive material, which comprises processing a silver halide photographic light-sensitive material using the silver halide photographic light-sensitive material processing agent according to claim 1. 5. A silver halide photographic light-sensitive material is processed in an automatic processor having at least a developing tank, a fixing tank, a water washing tank or a stabilizing tank, and a drying section while replenishing at least a developing replenisher, and the developing replenisher is replenished. The method for processing a silver halide photographic light-sensitive material according to claim 4, wherein the replenishing amount of the solution is 50 to 300 ml per 1 m ^{2 of the} light-sensitive material to be processed.