JPH0887093A - Method for developing silver halide black-and-white photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain a sufficiently contrasty negative picture with a developer stable at >pH11.0, to reduce the variation of photographic performance even with a small replenishment of developer and to obtain a stabilized performance at all times by allowing the development initiator and replenished developer to contain a developing agent and specifying the replenishment of the development initiator and developer. CONSTITUTION: A photosensitive silver halide emulsion layer is provided on a substrate, and a hydrzine derivative shown by formula I or II is incorporated into the emulsion layer or the other hydrophilic colloid layer. The development initiator and replenished developer contain a dihydroxybenzene-base developing agent and an auxiliary developing agent exhibiting superadditivity with the agent, and the pH is increased by <=0.25 when 0.1mol of sodium hydroxide is added to l of the liq. The development initiator is kept at pH9.5-11.0, and the replenishment of the developer is controlled to <=225ml/m<2> . In the formulas, A is aryl or heterocyclic ring group, (n) is an integer of 1 or 2, R1 and R2 are hydrogen atom, alkyl, etc., and R3 is alkinyl or saturated heterocyclic ring group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a development processing method using a silver halide photographic light-sensitive material to form an ultrahigh contrast image at a pH of less than 11.0. The present invention relates to a less developing method.

[0002]

2. Description of the Related Art In the field of graphic arts, photographic characteristics of ultra-high contrast (especially gamma of 10 or more) are used in order to improve reproduction of continuous tone images or halftone images by halftone dot images. Is required. As a method for obtaining high-contrast photographic characteristics, a lithographic development method utilizing a so-called "infectious development effect" has been used for a long time, but it has a drawback that the developer is unstable and difficult to use.

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,7.
No. 27 (developer combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,
No. 386,831 (containing β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers), No. 2,419,975, and Mees.
The Theory of Photographic Process
Theory of the Photographic Process) 3rd Edition (196
6 years) 281 pages, etc. Among these, in particular, in US Pat. No. 2,419,975, it is possible to obtain a high-tone negative image by adding a hydrazine compound.
It is disclosed. In the patent specification, a hydrazine compound was added to a silver chlorobromide emulsion to obtain a high pH of 12.8.
It is described that when developed with the developing solution of No. 2, extremely high photographic characteristics with a gamma (γ) of more than 10 can be obtained.
However, a strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use.
Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. In JP-A-1-179939 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group was used to obtain a pH of 11 A processing method of developing with a developing solution of 0.0 or less is described. However, when a compound having an adsorbing group is added to a silver halide emulsion, the photosensitivity may be impaired if the amount exceeds a certain limit.
Since it has the effect of suppressing development or hindering the action of other useful adsorptive additives, the amount used is limited and sufficient contrast cannot be achieved. JP 60-1
No. 40340 discloses that the addition of amines to a silver halide photographic light-sensitive material improves the contrast. However, in the case of developing with a developer having a pH of less than 11.0, sufficient contrast cannot be expressed. JP-A-56-106244 discloses adding an amino compound to a developer having a pH of 10 to 12 to promote contrast. However, when amines are used by adding them to a developing solution, there are problems such as odor of the solution and stains due to adhesion to equipment used, or environmental pollution due to waste solution, and it is desired to incorporate it into a light-sensitive material. It has not yet been found that it can be added to a light-sensitive material to obtain sufficient performance.

US Pat. No. 4,998,604, and US Pat.
No. 94365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However,
As is clear from these examples, the contrast is not sufficient, and it is difficult to obtain the contrast and the required Dmax under practical development processing conditions.

In order to obtain a super-high contrast image by using a stable developing solution having a pH of less than 11.0, various investigations have been carried out and a specific hydrazine nucleating agent and a specific quaternary onium salt nucleation promoting agent are contained in a light-sensitive material. It has been found that a super-high contrast image can be obtained by using the agent together. However, even in this method, the replenishing amount of the developing solution is required to be about 320 to 450 ml when processing 1 square meter of the silver halide photographic light-sensitive material, and a further replenishing amount reducing method and a stable processing method are desired. When the replenishment amount is reduced, there is a problem that silver sludge in the developing tank increases and adheres to the photosensitive material.

It is known to reduce the change in photographic performance by reducing the change in pH value of the developer,
Stabilizing photographic performance by increasing the buffering capacity of a developing solution is disclosed in Japanese Patent Publication No. 3730/1993.

It is known to supply a developing solution as a solid processing agent, and JP-A-61-259921 describes that the stability of the developing solution as a solid processing agent is enhanced. Further, JP-A-5-265147 discloses a processing method in which a developing solution for processing a hydrazine-containing photosensitive material is supplied as a solid processing agent, and it is disclosed that black spots are improved.

[0008]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a sufficiently hard negative image with a stable developing solution having a pH of less than 11.0 and to improve the photographic performance with a small replenishing amount of the developing solution. It is an object of the present invention to provide a development processing method for a silver halide black-and-white photographic light-sensitive material which has a small fluctuation and can always obtain stable performance.

[0009]

The object of the present invention is to have at least one light-sensitive silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material containing at least one hydrazine derivative represented by the following general formula (1) or general formula (2) in the emulsion layer or other hydrophilic colloid layer is imagewise exposed to a developer. In the method of developing while replenishing the developing solution, the developing starter solution and the developing replenisher solution contain a dihydroxybenzene-based developing agent and an auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene type developing agent, and 0.1
The pH increase when the molar sodium hydroxide was added was 0.
It is a liquid having a property of 25 or less, and p
H was 9.5 to 11.0, and the replenishment rate of the developing replenisher was 225 ml / m ² or less. General formula (1)

[0010]

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General formula (2)

[0012]

[Chemical 9]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n
Represents an integer of 1 or 2. When n = 1, R ₁ and R
₂ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an aryloxy group,
Alternatively, it represents a heterocyclic oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. When n = 2, R ₁ and R
₂ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group,
It represents a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic oxy group. However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Shall represent a group. R ₃ represents an alkynyl group or a saturated heterocyclic group. The compound represented by the general formula (1) or the general formula (2) includes -NHNH in the formula.
At least one H of -includes those in which a substituent is substituted.

The general formulas (1) and (2) will be described in more detail. A represents an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.).

R ₁ and R ₂ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, Pentadienyl etc.), alkynyl group (eg propargyl, butynyl, pentinyl etc.),
Aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, unsaturated heterocyclic groups such as pyridine, thiophene, furan and saturated heterocyclic groups such as tetrahydrofuran, sulfolane),
Hydroxy group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, ,
Phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), and when n = 1, R ₁ and R ₂ together with the nitrogen atom form a ring (eg, piperidine, piperazine). , Morpholine, etc.).

However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, alkynyl group, saturated heterocyclic group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or hetero. It represents a ring oxy group. Specific examples of the alkynyl group and the saturated heterocyclic group represented by R ₃ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, an arboxy group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

In each of the general formulas, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group.
As the anti-diffusion group, a ballast group commonly used in non-moving photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption-promoting group include thiourea group, thiourethane group, heterocyclic thioamide group, mercaptoheterocyclic group, triazole group and the like, US Pat.
The groups described in No. 108 are mentioned.

--NHNH-- in the general formulas (1) and (2)
H, that is, the hydrogen atom of hydrazine is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg acetyl, trifluoroacetyl,
It may be substituted with a substituent such as ethoxycarbonyl) and an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.), and the compounds represented by the general formulas (1) and (2) include such compounds.

More preferred compounds in the present invention are compounds of the general formula (1) when n = 2, and compounds of the general formula (2)
Is a compound of.

In the compound of the general formula (1) with n = 2,
R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkenyl group,
An alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group,
A compound which is a hydroxy group or an alkoxy group and at least one of R ₁ and R ₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is more preferable.

Typical compounds represented by the above general formulas (1) and (2) are shown below. However, as a matter of course, the specific compounds of the general formulas (1) and (2) that can be used in the present invention are not limited to these compounds.

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

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

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

Examples of the nucleation accelerator used in the present invention include amine compounds, hydrazine compounds, quaternary onium salt compounds and carbinol compounds, with amine compounds and carbinol compounds being preferred. These nucleation accelerators are disclosed in JP-A-4-56749 and JP-A-63-163.
124045 gazette and the thing described in the same 62-187340 gazette are mentioned. These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule. Other specific examples include the compounds described in the following patents. Japanese Patent Application No. 3-295926, 3
It is a compound described in the specification of -293366.

More specifically, the following nucleation accelerators are listed, but the present invention is not limited thereto.

[0031]

[Chemical 13]

[0032]

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[0033]

[Chemical 15]

In the present invention, the compounds represented by the general formulas (3) and (4) are more preferably used as the accelerator.

The general formula (3) will be described in detail.

In the general formula (3), the groups represented by R ₁ and R ₂ are each an alkyl group (eg, methyl,
Ethyl, propyl, isopropyl, butyl, octyl,
Dodecyl etc.), alkenyl group (eg allyl, butenyl etc.), alkynyl group (eg propargyl, butynyl etc.)
Etc. These are further substituents (for example, aryl group, alkoxy group, aryloxy group, hydroxyl group, alkylthio group, arylthio group, sulfonamide group, carbonamido group, ureido group, sulfamoyl group, carbamoyl group, amino group, alkoxycarbonyl group, R ₁ may be substituted with R ₁
And R ₂ to form a ring (eg piperidine, piperazine,
Morpholine, pyrrolidine, etc.) may also be formed. As R ₁ and R ₂ , an alkyl group is preferable and the carbon number is 2 to 20.
Most preferred are alkyl groups of

The group represented by R ₃ includes an alkyl group (eg, methyl, ethyl, propyl, t-butyl, octyl, dodecyl, etc.), an alkenyl group (eg, allyl, butenyl, etc.), an alkynyl group (eg, propargyl, butynyl, etc.). Etc.), aryl groups (eg phenyl, naphthyl etc.),
Or a heterocyclic group (eg, thienyl, furyl, pyridyl, etc.) and the like.

These may be further substituted with the same substituents as those described for R ₁ and R ₂ .

L ₁ is a divalent linking group, preferably a group having an optionally substituted alkylene group (provided that the alkylene group is

[0040]

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Combined with).

Among the divalent linking groups represented by L ₁ , more preferable ones are an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 1 to 10 carbon atoms and the groups shown below. A group consisting of a combination may be mentioned.

[0043]

[Chemical 17]

X is

[0045]

[Chemical 18]

Represents

L ₂ represents an alkylene group (eg, methylene, ethylene, propylene, butylene, etc.) or an alkenylene group (eg, propenylene, butenylene, etc.), preferably an alkylene group having 1 to 4 carbon atoms, and a more preferred group is Examples thereof include a methylene group and an ethylene group. Y represents a carbonyl group, a sulfonyl group, a sulfoxy group, or a phosphoryl group, and a carbonyl group or a sulfonyl group is preferable. L ₃ is

[0048]

[Chemical 19]

Represents

Z ₁ , Z ₂ and Z ₃ are each a hydrogen atom,
It represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Each of Z ₁ , Z ₂ and Z ₃ is preferably a hydrogen atom, an alkyl group or an aryl group.

N represents 0 or 1.

Specific examples of the compound represented by formula (3) are shown below, but the invention is not limited thereto.

[0053]

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[0054]

[Chemical 21]

[0055]

[Chemical formula 22]

[0056]

[Chemical formula 23]

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

[0059]

[Chemical formula 26]

[0060]

[Chemical 27]

[0061]

[Chemical 28]

[0062]

[Chemical 29]

The general formula (4) will be described in detail.

In the general formula (4), the groups represented by R ₁ and R ₂ are each an alkyl group (eg, methyl,
Ethyl, propyl, isopropyl, butyl, octyl,
Dodecyl etc.), an alkenyl group (eg allyl, 2-methylallyl, butenyl etc.), an alkynyl group (eg propargyl, butynyl etc.) and the like. These are further substituted (for example, alkyl group, aryl group, alkoxy group, aryloxy group, hydroxyl group, alkylthio group, arylthio group, sulfonamide group, carbonamide group, ureido group, sulfamoyl group, carbamoyl group, amino group, alkoxy group. It may be substituted with a carbonyl group, a carboxyl group, etc.) and may be linked with R ₁ and R ₂ to form a ring (eg piperidine, piperazine, morpholine, pyrrolidine, etc.). As R ₁ and R ₂ ,
An alkyl group and an alkenyl group are preferable, and an alkyl group having 2 to 20 carbon atoms and an alkenyl group having 3 to 20 carbon atoms are preferable.

The group represented by R ₃ is an alkyl group (eg, methyl, ethyl, propyl, butyl, octyl, dodecyl, etc.), an alkenyl group (eg, allyl, butenyl, etc.), an alkynyl group (eg, propargyl, butynyl, etc.). An aryl group (eg, phenyl, naphthyl, etc.),
Or a heterocyclic group (eg, thienyl, furyl, pyridyl, etc.) and the like.

These may be further substituted with the same substituents as described for R ₁ and R ₂ .

Among the compounds of the general formula (4), more preferable ones are the following general formulas (4-A) and (4-B).
Compounds of

[0068]

[Chemical 30]

In the formula, R ₁ , R ₂ , Y and l have the same meanings as those in formula (4). L represents a divalent aliphatic group, J ₁ and J ₂ represent a divalent linking group, and m and n represent 0 or 1. R represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

Examples of the divalent aliphatic group represented by L include an alkylene group (preferably having 1 to 20 carbon atoms) and an alkenylene group (preferably having 3 to 20 carbon atoms). Is preferably an alkylene group, and more preferably an alkylene group having 2 to 10 carbon atoms.

Most preferably, L is ethylene, trimethylene or tetramethylene.

L may be further substituted with an appropriate substituent (eg, alkyl group, aryl group, etc.).

The divalent linking group represented by J ₁ and J ₂ is a group consisting of the groups shown below, a group consisting of a combination of the groups shown below, and a substituent suitable for them (for example, an alkyl group,
Alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic onium group, amino group, ammonium group,
Acylamino group, carbamoyl group, sulfonamide group,
Sulfamoyl group, ureido group, alkoxy group, aryloxy group, heterocyclic oxy group, hydroxyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, sulfo group Groups, carboxyl groups, acyloxy groups, acyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, nitro groups, thioacyl groups, thioacylamino groups, thioureido groups, etc.).

--CH _2- , --CH = CH--, --C ₆ H ₄
-, _{pyridinediyl, -N (Z 1) - (} Z 1 is a hydrogen atom,
Represents an alkyl group or an aryl group), -O-, -S
-, - CO -, - SO 2 -, - CH = N-, m and n
Each represent 0 or 1, but both are most preferably 0.

Y is an alkylene group (eg ethylene, propylene, trimethylene, tetramethylene etc.), an alkenylene group (eg vinylene, propenylene, 1-butenylene, 2-butenylene etc.), an arylene group (eg phenylene etc.), and A group having an appropriate substituent (for example, those mentioned above as the appropriate substituents of J ₁ and J ₂ ) is shown.

Y is preferably an alkylene group, more preferably an ethylene, propylene or trimethylene group.

The aliphatic group represented by R is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group (preferably an alkyl group having 1 to 20 carbon atoms in the alkyl portion and alkenyl or alkynyl portion). Number 2
20 alkenyl groups and alkynyl groups).

The aromatic group represented by R is preferably a monocyclic (eg benzene etc.) or condensed ring (eg naphthalene etc.) aryl group.

The heterocyclic group represented by R is preferably a monocycle or a condensed ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, and is preferably a 5-membered ring (eg pyrrole, thiophene, furan). , Imidazole, pyrazole, thiazole, oxazole, thiadiazole, oxadiazole, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazolidine, tetrahydrofuran, etc., 6-membered ring (for example, pyridine, pyrazine,
Pyrimidine, pyridazine, triazine, dithiin, dioxine, piperidine, morpholine, quinuclidine, etc. and these and a cycloalkyl ring (for example, cyclopentane,
Condensation with cyclohexane, cycloheptane etc.), cycloalkenyl ring (eg cyclopentene, cyclohexene, cycloheptene etc.), aromatic ring (eg benzene, naphthalene etc.) and heterocycle (eg pyrrole, imidazole, pyridine, pyrazine, pyrimidine etc.) Rings are preferred.

Next, specific examples of the compound represented by formula (4) of the present invention are shown below, but the present invention is not limited thereto.

[0081]

[Chemical 31]

[0082]

[Chemical 32]

[0083]

[Chemical 33]

[0084]

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[0085]

Embedded image

[0086]

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The amount of the nucleation accelerator added is not particularly limited as long as it is used in a necessary amount depending on the characteristics of the light-sensitive material.
When used in the present invention, the preferable addition amount is 1 × 10 ⁻⁵
˜2 × 10 ⁻² mol / molAg, more preferably 2 × 10 ^{−5 −1}
× 10 ^-2 mol / mol Ag.

A suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve, etc. is used. be able to. In addition, by the well-known emulsion dispersion method,
It is also possible to use an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare an emulsion dispersion for use. Alternatively, it can be used as a fine dispersion by a method known as a solid dispersion method.

The halogen composition of the silver halide emulsion used in the present invention has a silver chloride content of 50 mol% or more, silver chloride, silver chlorobromide, and chloroiodo in order to more effectively achieve the object of the present invention. Silver bromide is preferred. The silver iodide content is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, the light-sensitive material suitable for high-illuminance exposure such as scanner exposure and the light-sensitive material for line drawing are
It contains a rhodium compound in order to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium ( III) Complex salt, trisalathodium (II
I) Complex salts and the like can be mentioned. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. The addition amount is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograp by P. Glafkides.
hique (Paul Montel, 1967), GFDufin
By Photographic Emulsion Chemistry (The Focal Pres
s, 1966), by VL Zelikman et al Making and
Coating Photographic Emulsion (The Focal Press
, 1964) and the like.

As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
0, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 2
It is 0% or less, particularly preferably 15% or less. Average grain size of grains in monodisperse silver halide emulsion is 0.5 μm
It is below, and particularly preferably 0.1 μm to 0.4 μm.

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

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

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

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

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

In the present invention, a silver halide emulsion particularly suitable as a reversal light-sensitive material is a silver halide comprising 90 mol% or more, more preferably 95 mol% or more, and silver bromide of 0 to 10 is contained. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

Further, the silver halide emulsion used in the light-returning light-sensitive material of the present invention preferably contains a transition metal complex. Transition metals include Rh, Ru, Re, Os, I
r, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, seleno Cyanate ligands, tellurocyanate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of preparing particles. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium complex compound such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salts, sodium salts, potassium salts, etc.). The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol to 1.0
× 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl ₅ ] ^-2 6 [Re (NO) CN ₅ ] ^-2 7 [Re (NO) ClCN ₄ ] ^-2 8 [Rh (NO) ₂ Cl ₄ ] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl ₅ ] ^-2 14 [Cr (NO) Cl ₅ ] ^-3 15 [Re (NO) Cl ₅ ] ^-1 16 [Os (NS) Cl ₄ (TeCN)] ^-2 17 [Ru (NS) I ₅ ] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The spectral sensitizing dye used in the present invention is not particularly limited. The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but it is used in the range of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount range of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol is preferable per 1 m ² of the surface area of the silver halide grain. , Especially 6.5 × 10 ^{−7 to} 2.0 ×
The addition amount range of 10 ⁻⁶ mol is preferable.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in Section 1X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, as for A) an argon laser light source, JP-A-60-1
No. 62247, JP-A-2-48653, US Pat.
161,331, West German Patent 936,071, and Japanese Patent Application No. 3-189532, simple merocyanines,
B) For helium-neon laser light sources, JP-A-50-62425, 54-18726, and 59-
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398.
No. 18, JP-A-62-284343, JP-A-2-10
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
No. 32, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242 and JP-A-3-67242, and general formula (IIIa) and general formula (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978)
Monthly publication) It is described on page 23, IV, section J.

[0103]

Embedded image

[0104]

[Chemical 38]

In addition to the above, the helium-neon light source is represented by the general formula (I) described in Japanese Patent Application No. 4-228745, page 8, line 1 to page 13, line 4 to line 4. Particularly preferred are sensitizing dyes. Specific examples are shown below, but in addition to these, any of those described in the general formula (I) of Japanese Patent Application No. 4-228745 is preferably used.

[0106]

[Chemical Formula 39]

[0107]

[Chemical 40]

The following dyes are particularly preferably used for the LED light source and the infrared semiconductor laser.

[0109]

Embedded image

[0110]

Embedded image

The following dyes are preferably used for the infrared semiconductor laser light source.

[0112]

[Chemical 43]

[0113]

[Chemical 44]

[0114]

[Chemical formula 45]

The sensitizing dye of the general formula (IV) described in Japanese Patent Application No. 5-201254 (from page 20, line 14 to page 22, line 23) is preferably used for a white light source for photographing with a camera. . Specific compound examples are shown below.

[0116]

[Chemical formula 46]

[0117]

[Chemical 47]

[0118]

[Chemical 48]

[0119]

[Chemical 49]

The silver halide light-sensitive material of the present invention contains a dihydroxybenzene type developing agent as a developing agent and an auxiliary developing agent exhibiting superadditivity therewith and having a pH of 9.5 to 1.
Development processing is performed with a developing solution of 1.0. In the development processing, a usual automatic development processor can be used. The developing solution filled in the development processing tank at the start of development is called a development starting solution (mother solution), and the developing solution replenished in the development processing tank at the time of continuous development is called a development replenishing solution. In the present invention, both the development starter solution and the development replenisher solution contain, as a developing agent, a dihydroxybenzene type developing agent and an auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene type developing agent.

Examples of the dihydroxybenzene type developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone and hydroquinone monosulfonate, and hydroquinone is particularly preferable. As the auxiliary developing agent showing superadditivity with the dihydroxybenzene type developing agent, 1-
There are phenyl-3-pyrazolidones and p-aminophenols. Therefore, in the present invention, a combination of a dihydroxybenzene-based developing agent and 1-phenyl-3-pyrazolidones or a combination of a dihydroxybenzene-based developing agent and p-aminophenols is preferably used. Examples of the developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone and the like. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-
(Hydroxyphenyl) glycine, etc., but especially N
-Methyl-p-aminophenol is preferred. The dihydroxybenzene type developing agent is usually 0.05 to 0.8 mol /
It is preferably used in an amount of 1 liter, but in the present invention, it is particularly preferably used in an amount of 0.23 mol / liter or more. More preferably, 0.23 to 0.6 mol /
It is in the liter range. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.23.
~ 0.6 mol / liter, more preferably 0.23 ~
0.5 mol / liter, the latter 0.06 mol / liter or less, more preferably 0.03 mol / liter to 0.
It is preferably used in an amount of 003 mol / l.

In the present invention, both the development initiating solution and the development replenishing solution have the property that "the pH rise when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.25 or less". It is necessary. The method of confirming that the development starter solution or development replenisher used has this property is as follows.
Is adjusted to 10.5, and then 0.1 mol of sodium hydroxide is added to 1 liter of this solution, and the pH value of the solution at this time is measured. It is determined that it has the property. In the present invention, it is particularly preferable to use a development starter solution and a development replenisher solution which have a pH value increase of 0.2 or less when the above test is carried out.

As a method for imparting the above-mentioned properties to the development initiating solution and the development replenishing solution, it is preferable to use a buffer.
Examples of the buffering agent include carbonate, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg saccharose), oximes (eg acetoxime), phenols (eg 5 -Sulfosalicylic acid), a third phosphate (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The amount of buffer, especially carbonate, used is preferably
0.5 mol / liter or more, particularly 0.5 to 1.5 mol /
It is a liter.

In the present invention, the pH of the development initiating solution is 9.5 to 11.0, particularly preferably 9.8 to 1.
It is in the range of 0.7. The pH of the developer replenisher and the pH of the developer in the developing tank during continuous processing are also within this range. p
As the alkali agent used for setting H, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

When processing 1 square meter of the silver halide photographic light-sensitive material, the replenisher amount of the developer is 225 ml or less, preferably 225 to 30 ml, and particularly 1
80 to 50 ml. The development replenisher may have the same composition as the development starter, or may have a higher concentration of components consumed in the development than the starter.

Additives (eg, preservatives) usually used in the developing solution (both the development initiating solution and the developing replenishing solution are collectively referred to as a developing solution, hereinafter) when developing the light-sensitive material in the present invention. , A chelating agent). Examples of preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. 0.2 for sulfite
It is used in an amount of 0 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is preferably 1.2 mol / liter. Particularly preferably, it is 0.35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Here, the ascorbic acid derivative includes ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof. It is preferable to use sodium erythorbate in terms of material cost. The addition amount is 0.03 to molar ratio based on the dihydroxybenzene type developing agent.
The range of 0.12 is preferable, and particularly preferably 0.05 to
It is in the range of 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Additives other than those mentioned above include
Development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or its derivatives; mercapto Compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds may be included as antifoggants or black pepper inhibitors. Specifically, 5-nitroindazole,
5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5- Nitrobenztriazole, 4
-[(2-Mercapto-1,3,4-thiadiazole-
Examples thereof include sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution.

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

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

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

Organic phosphonocarboxylic acids include those disclosed in JP-A Nos. 52-102726, 53-42730 and 54.
-112127, 55-4024, 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts.

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

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

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

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

Further, as a silver stain preventing agent in a developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, the compound described in JP-A-62-212651 can be used as the development unevenness preventing agent, and the compound described in JP-A-61-267759 can be used as the dissolution aid. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained. The development temperature and time are interrelated and are determined in relation to the total processing time, but generally the development temperature is from about 20 ° C to about 50 ° C.
C., preferably 25 to 45.degree. C., development time 5 seconds to 2
Minutes, preferably 7 seconds to 1 minute 30 seconds.

It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid,
An aqueous solution containing citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid, tyrone, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid. From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained.
As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter.
If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH adjuster (eg,
(Ammonia, sulfuric acid), a chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants, and JP-A-57-6.
The amphoteric surfactants described in Japanese Patent No. 740 can be used.
Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include JP-B-45-35754, 58-122535 and 58.
-122536, thiourea derivatives, alcohols having a triple bond in the molecule, U.S. Pat. No. 4,126,45.
Thioether compounds described in JP-A No. 4-22986
Examples thereof include mesoionic compounds described in No. 0, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, oxalic acid citric acid, maleic acid, glycolic acid and adipic acid, and inorganic buffers such as boric acid, phosphate and sulfite. Agents can be used. Acetic acid, tartaric acid, and sulfite are preferably used. PH here
The buffer is used for the purpose of preventing the pH of the fixing agent from rising due to the carry-in of the developing solution, and is 0.01 to 1.0 mol / liter,
More preferably, about 0.02-0.6 mol / liter is used. The pH of the fixing solution is preferably 4.0 to 6.5, and particularly preferably 4.5 to 6.0. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 ° C.
~ 45 ° C, fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is 600 ml / m ² or less, and particularly preferably 500 ml / m ² or less with respect to the processing amount of the light-sensitive material.

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. For washing or stabilizing treatment, the amount of washing water is usually ² per 1 m ^{2 of} silver halide light-sensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
It can also be carried out by including, that is, washing with water. That is, not only water saving processing becomes possible, but also piping for installing the automatic processing machine can be eliminated. As a method of reducing the replenishment amount of flush water, a multistage countercurrent method (for example, 2
Stages, 3 stages, etc.) are known. When this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed. Washed with water. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide washing tanks for squeeze rollers and crossover rollers described in No. 350 and No. 62-287252. Alternatively, addition of various oxidizing agents and filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the method according to the present invention is disclosed in JP-A-60- 23
As described in No. 5133, it can also be used for a processing solution having a fixing ability, which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in the washing tank. In addition, in some cases, stabilization treatment may be performed following the water washing treatment,
As examples thereof, JP-A-2-201357 and JP-A-2-132
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time is 0-5
0 ° C. and 5 seconds to 2 minutes are preferable.

The processing liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Instead of the water washing step, four stable steps may be used.

The components of the developer or fixer, excluding water, may be supplied in solid form and dissolved in a predetermined amount of water before use to be used as a developer or fixer. The treating agent having such a form is called a solid treating agent. The solid processing agent is
Powders, tablets, granules, powders, lumps or pastes are used, and the preferred form is JP-A-61-259921.
The form or tablet described in No. The tablet manufacturing method is
For example, JP-A-51-61837 and JP-A-54-15503.
No. 8, No. 52-88025, British Patent Nos. 1,213,8.
No. 08, etc., and the granule-treating agent can be produced by, for example, JP-A Nos.
109043, 3-39735 and 3-397.
It can be produced by a general method described in No. 39, etc. Further, the powder treating agent is disclosed in, for example, JP-A-54-133332.
Nos. 725,892 and 729,862, and German Patent 3,733,861.

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

In the preparation of the solid processing agent, at least two mutually reactive particulate materials among the materials constituting the processing agent and at least one interposition of a material inert to the reactive material are used. It is also possible to employ a method in which the reactive substances are arranged in layers so as to form layers separated by the separation layer, a vacuum-packable bag is used as the packaging material, and the bag is evacuated and sealed. As used herein, the term inert means that the substances do not react under normal conditions in the package when they are in physical contact with each other, or if any reaction is not significant. The inert substance, apart from being inert to the two mutually reactive substances, need only be inert in the intended use of the two reactive substances. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react with each other in the developer in direct contact, they can be stored in the package for a long time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. Used as packaging materials for these vacuum packaging materials are bags made from a laminate of inert plastic film, plastic material and metal foil.

There are no particular restrictions on various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item 1) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to right lower column, line 7 and JP-A-2-18542, page 2, lower left column 13 From line 4 to page 4, lower right column, line 18. 2) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A 1-237538. Thiosulfinic acid compounds described in the public notice. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 5) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 7) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Monomethine compound Compounds of general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 11) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12 lower left column, and EP452772A.

[0146]

EXAMPLES The present invention will be described in more detail with reference to the following examples. First, a method of making a silver halide emulsion used in the following examples will be described. Emulsion-A 0.13 M silver nitrate aqueous solution and 1.5 × per mol of silver
K ₂ Rh (H ₂ O) Cl ₅ and 2 corresponding to 10 ^-7 mol
Containing K ₃ IrCl ₆ corresponding to × 10 ⁻⁷ mol,
An aqueous solution of a halogen salt containing M potassium bromide and 0.09 M sodium chloride is added to an aqueous gelatin solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione with stirring at 38 ° C. for 12 minutes by the double jet method. Nucleation was carried out to obtain silver chlorobromide grains having an average grain size of 0.14 μm and a silver chloride content of 70 mol%. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, 0.26 M potassium bromide, and a halogen salt aqueous solution containing 0.65 M sodium chloride were added over 20 minutes by the double jet method. Then 1 × 10 ^-3 mol K
Solution I was added for conversion, followed by washing with water by the flocculation method according to a conventional method using a copolymer of isobutene and monosodium maleate as a precipitating agent, and 40 g of gelatin per 1 mol of silver was added to adjust the pH.
6.5, pAg 7.5, and then, per mol of silver, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, and 2 parts of potassium thiocyanate.
00 mg and sodium thiosulfate 5 mg were added, and the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization, and then as a stabilizer 4-
150 mg of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained grains were silver iodochlorobromide cubic grains having an average grain size of 0.25 μm and a silver chloride content of 69.9 mol%. (Variation coefficient 10%) Emulsion-B 0.37 mol of silver nitrate aqueous solution and (NH ₄ ) ₃ RhCl corresponding to 1.0 × 10 ⁻⁷ mol per mol of silver in the finished emulsion.
_An aqueous halogen salt solution containing ₆ and 2 × 10 ⁻⁷ mol of K ₃ IrCl ₆ , 0.11 mol of potassium bromide and 0.27 mol of sodium chloride was added to sodium chloride and 1,3-dimethyl-2-imidazolidinethione. Nucleation is carried out by adding the mixture to a gelatin aqueous solution containing at 80 ° C. for 12 minutes at 45 ° C. by the double jet method to obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 70 mol%. It was Then, similarly, a 0.63 mol silver nitrate aqueous solution, a 0.19 mol potassium bromide, and a 0.47-mol sodium chloride containing halogen salt aqueous solution were added over 20 minutes by the double jet method. Thereafter, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver, conversion was carried out, and the product was washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added, pH 6.5, pAg 7.5
In addition, 7 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added per 1 mol of silver, and the mixture was heated at 60 ° C. for 45 minutes to be chemically sensitized and treated with 4-hydroxy- as a stabilizer. 150 mg of 6-methyl-1,3,3a, 7-tetrazaindene and proxel as preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Variation coefficient 9%) Emulsion-C 2 solutions and 3 solutions were simultaneously added to 1 solution of Table 1 kept at 38 ° C. and pH 4.5 over 24 minutes while stirring, and then 0.
18 μm particles were formed. Subsequently, the liquids 4 and 5 in Table 1 were added over 8 minutes, and 0.15 g of potassium iodide was added to complete the particle formation. Then, after washing with water by the flocculation method according to a conventional method and adding gelatin, p
H was adjusted to 5.2 and pAg 7.5, sodium thiosulfate 4 mg, N, N-dimethylselenourea 2 mg and chloroauric acid 1
Add 0 mg and 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenethiosulfinate,
It was chemically sensitized to obtain the optimum sensitivity at ℃. Furthermore, as a stabilizer, 2-methyl-4-hydroxy-1,3,3a,
50 mg of 7-tetraazaindene and phenoxyethanol as a preservative were added so as to be 100 ppm, and finally 80 mol% of silver chloride was contained, and the average particle size was 0.20 μm.
m silver iodochlorobromide cubic grains were obtained. (Coefficient of variation 9%)

[0147]

[Table 1]

Example 1 Undercoat layer (0.5 μm) made of vinylidene chloride copolymer
Polyethylene terephthalate film having (150
μm) on the support, from the support side, UL, EM, ML,
It was applied so as to have a PC layer structure. The preparation method and coating amount of each layer are shown below.

(UL) 10 g of gelatin, 50 wt% of gelatin, 3.5 wt% of polyethyl acrylate latex compound (a) were added to gelatin, and water was added so that the final amount was 250 ml. , Gelatin was applied at 0.4 g / m ² .

(EM) The above emulsion-A was mixed with gelatin 4
After dissolution at 0 ° C., sensitizing dye (S5-9 above) was added to 3.
2.times.10.sup.- ⁴ mol / mol Ag and sensitizing dye (S-1) 2.
7 × 10 ⁻⁴ mol / mol Ag, KBr 3.4 × 10 ⁻³ mol / mol Ag, compound (b) 3.2 × 10 ⁻⁴ mol / mol A
g, compound (c) 7.4 × 10 ⁻⁴ mol / mol Ag, hydroquinone 9.7 × 10 ⁻³ mol / mol Ag, phosphoric acid 8.
0 × 10 ⁻³ mol / mol Ag, 5 × 10 ⁻⁴ mol / mol Ag of the hydrazine derivative shown in Table 2, 8 × 10 ⁻⁴ mol / mol Ag of the nucleation accelerator shown in Table 2, Compound W-1 3 x 10
^{-Add 4} mol / mol Ag, and add 15 to gelatin.
1 wt% for polyethyl acrylate and gelatin
5 wt% latex copolymer (methyl acrylate; 2-acrylamido-2-methylpropanesulfonic acid sodium salt; 2-acetoacetoxyethylmethacrylate = 88: 5: 7 weight ratio), 4w with respect to gelatin
The compound (a) of t% was added, and the coating was performed so that Ag was 3.3 g / m ² .

[0151]

[Table 2]

Compound (d) 7 was added to (ML) gelatin solution.
mg / m ² , 15 wt% of polyethyl acrylate to gelatin, and 3.5 wt% of compound (a) to gelatin were added so that gelatin was 0.5 g / m ² .

[0153] (PC) to the gelatin solution, the average particle size 3.5μm of an amorphous SiO ₂ matting agent 40 mg / m ^2, silicone oil 20 mg / m ² and the compound as a coating aid (e) 5 mg / m ² and dodecyl 25 mg / m ² of sodium benzenesulfonate was added and coated. 0.3 for gelatin
g / m ² .

Additives to the light-sensitive material layer of Example 1

[0155]

Embedded image

The back layer and the back protective layer were coated by the following formulation. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant P-sodium dodecylbenzenesulfonate 40 mg / m ² compound [a] 110 mg / m ² SnO ₂ / Sb (weight ratio 90 / 10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² dye [b] 100 mg / m ² dye [c] 50 mg / m ²

[0157]

[Chemical 51]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzene sulfonate sodium 15 mg / M ² Sodium acetate 40mg / m ²

A developing solution was prepared according to the formulation shown in Table 3.

[0160]

[Table 3]

The fixer formulation used in the present invention is shown below. (Fixer formulation) Ammonium thiosulfate 360 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium sulfite 75.0 g Sodium hydroxide 37.0 g Glacial acetic acid 87.0 g Tartaric acid 8.8 g Sodium gluconate 5.2 g Aluminum sulfate 25.0 g Water to add 3 liter pH (adjusted with sulfuric acid or sodium hydroxide) 4.85

(Evaluation) The coated sample was exposed to 3200 ° K tungsten light using an optical wedge. Next, these samples were used as FG-68 manufactured by Fuji Photo Film Co., Ltd.
A running test was performed using 0A. The running conditions are the size of a large sheet of paper half exposed (50.8 cm).
Forty rounds of film A having a size of 60.1 cm) were processed and run for 6 days and rested for 1 day. The replenishment amount is shown in Table 3. Development time = 3
It was processed at 0 ″ and temperature = 35 ° C.

The evaluation of photographic properties was performed as follows. The gradation is obtained by dividing the difference between density 3.0 and density 0.3 by the logarithm of the exposure amount giving density 3.0 and the logarithm of the exposure amount giving density 0.3. The reciprocal of the exposure dose required to obtain a density of 1.5 when treated with a new solution of D-1 of 3 is 10
It was shown as 0 as a relative value. The silver stain was visually evaluated on a scale of 5 levels. The state where no silver stains are generated on the film, the developing tank, or the roller is set as "5", and the silver stain is generated on the entire surface of the film, and a large amount of silver stains is also generated on the developing tank and the roller. " “4” is not generated in the film, but is slightly generated in the developing tank and the roller, but it is a practically acceptable level. "3"
The following is a practical problem or unacceptable level. Table 4 shows the results of photographic properties obtained by running experiments.

[0164]

[Table 4]

By the processing method using the hydrazine derivative of the present invention and the developing solution, a super-high contrast image can be stably obtained even if the processing is carried out with a low replenishing amount. Furthermore, when processing with a low replenishment amount, the amount of silver sludge generated in the developing tank increases, and transfer to the film also increases, but by using the developer of the present invention, silver stain during running is remarkably good. Turned into This effect was unexpected, and favorable results were obtained in which running stability was improved and silver stains were also improved.

Example 2 A sample was prepared in the same manner as in Example 1 except that the EM layer formulation of Example 1 was changed to the following.

(EM) The above emulsion-B was mixed with gelatin in 4 parts.
3. After dissolving at 0 ° C., add sensitizing dye (S1-1 above) to 4.
6 × 10 ⁻⁴ mol / mol Ag, sensitizing dye (S-1) 1.7
× 10 ^-4 mol / mol Ag, KBr4.5 × 10 ^-3 mol /
Mol Ag, compound (II) 3.1 × 10 ⁻⁴ mol / mol A
g, compound (c) 7.4 × 10 ⁻⁴ mol / mol Ag, hydroquinone 2.9 × 10 ⁻² mol / mol Ag, acetic acid 2.3
× 10 ^-3 mol / mol Ag, 10 wt% with respect to gelatin
Colloidal silica of 4 and hydrazine derivatives shown in Table 5
× 10 ⁻⁴ mol / mol Ag, 6 × the nucleation accelerator shown in Table 5
10 ^-4 mol / mol Ag, compound W-1 3.4 × 10 ^-4
Mol / mol Ag added, and further 30w against gelatin
4 wt% of the compound (ii) was added to t% polyethyl acrylate latex polymer and gelatin, and applied. The compounds (a), (b) and (c) are the same as in Example 1.

[0168]

[Table 5]

Using the sample thus prepared, 488
It was exposed to xenon flash light with an emission time of 10 ^-5 sec through an interference filter having a peak at nm and a continuous wedge. Next, these samples are used as FG manufactured by Fuji Photo Film Co., Ltd.
A running test was performed using -680AG. The running conditions are large full-size paper (5
0.8 x 61.0 cm) sample is processed for 40 sheets, and it runs for 6 days and rests for 1 day.
Went round.

Preparation of the developing solution was carried out from the storage forms of a solid processing agent and a liquid processing agent. Table 6 shows the formulation of the developer used and the storage form. In the method for producing the solid processing agent, the components of the developing solution were solidly laminated and packed in a bag made of an aluminum foil coated with a plastic material. From the top, the order of stacking is as follows: 1st layer Hydroquinone 2nd layer Other components 3rd layer Sodium bisulfite 4th layer Potassium carbonate 5th layer Potassium hydroxide pellets, evacuated in a conventional manner, and evacuated the system. Sealed. The liquid treatment agent is 1.5 times the prescription of the used liquid (dilution rate = 2:
It was stored in the concentrated solution of 1). Solid treatment and liquid treatment are 5
It was stored at 0 ° C. for 60 days, then dissolved and used for running.

The developing time was 30 seconds, and the developing temperature was 35 ° C. GR-F1 was used as the fixing solution, the replenishing amount was 120 ml per volume, and the fixing temperature was 37 ° C. The results and experimental conditions are shown in Table 5. The photographic property was evaluated in the same manner as in Example 1, and the uneven processing was evaluated by Dainippon Screen Co., Ltd.
Using an Argon Light Source Color Scanner SG708 manufactured by K.K., 90% flat mesh was output to the sample at 100 lines, and the processing unevenness was visually evaluated. Mura was sensory-evaluated by a 5-point method of (good) 5 to 1 (bad). For the evaluation of treatment unevenness, the sample was treated at the end of running.

[0172]

[Table 6]

[0173]

[Table 7]

It can be seen that the developer prepared from the solid processing agent is excellent in stability even in the processing with a low replenishing amount and the processing unevenness is good.

From the above results, pH = 1 according to the present invention.
To provide a processing method of a silver halide black-and-white photographic light-sensitive material capable of maintaining a stable performance in a developer having a super-high contrast image of less than 1.0, a small amount of silver stains even with a low replenishing amount processing and a small fluctuation of photographic properties. You can

Claims (4)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer, wherein the emulsion layer or other hydrophilic colloid layer has the following general formula (1) or general formula (2).
In the method of developing a silver halide photographic light-sensitive material containing at least one of hydrazine derivatives represented by, while developing the image while replenishing the developing solution, the developing starter solution and the developing replenishing solution are dihydroxybenzene-based developing agents and And an auxiliary developing agent exhibiting superadditivity, and said solution 1
A solution having a property that the pH increase when 0.1 mol of sodium hydroxide is added to liter is 0.25 or less, and the pH of the development initiating solution is 9.5 to 11.0. A method of developing a silver halide black and white photographic light-sensitive material, characterized in that the replenishing amount of the developing replenisher is 225 ml / m ² or less. General formula (1) General formula (2) In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n is 1 or 2
Represents the integer. When n = 1, R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
Aryl group, heterocyclic group, hydroxy group, alkoxy group,
It represents an alkenyloxy group, an aryloxy group, or a heterocyclic oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. When n = 2, R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
It represents an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Shall represent a group. R ₃ represents an alkynyl group or a saturated heterocyclic group. The compound represented by the general formula (1) or the general formula (2) includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent. 2. The development processing method according to claim 1, wherein the silver halide photographic light-sensitive material contains a nucleation accelerator. 3. The development processing method according to claim 2, wherein the nucleation accelerator is represented by the general formula (3) or the general formula (4). General formula (3) In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group, or an alkynyl group, and R ₁ and R ₂ may form a ring. R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. L ₁ represents a divalent linking group, and X is Represents L ₂ represents an alkylene group or an alkenylene group, Y represents a carbonyl group, a sulfonyl group, a sulfoxy group,
Represents a phosphoryl group. L ₃ is Represents Z ₁ , Z ₂ and Z ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n represents 0 or 1. General formula (4) In the formula, R ₁ , R ₂ and R ₃ are each an alkyl group,
Represents an alkenyl group or alkynyl group. However, the compound of the general formula (4) has a thioether group and It has a partial structure of. Y represents an optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted arylene group, and l represents an integer of 2 or more. 4. The developer contains 0.3 to 1.2 mol / liter of free sulfite ion and ascorbic acid derivative, and the concentration ratio of ascorbic acid derivative / dihydroxybenzene type developing agent is 0.03 to 0. The developing treatment method according to claim 1, wherein the developing treatment is performed with the developing solution of No. 12.