JPH11282134A - Treatment of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating method with excellent stability for long-term development in the treatment with a low replenishing amt. of a silver halide photographic sensitive material having a silver halide emulsion layer having a spectral max. in >=600 nm region. SOLUTION: In the developing treatment of a silver halide photographic sensitive material having a silver halide emulsion layer with the spectral max. in >=600 nm region, such a developer replenisher is used that the molar ratio of the developing assistant to the developing agent of the replenisher is >=1.1 times as the molar ratio of the developing assistant to the developing agent of the starting developer. The replenishing amt. is controlled to 50 ml/m<2> to 200 ml/m<2> . Further, a solid treating agent containing the developing agent is directly put in a developing tank during development. Or, a solid treating agent containing the developing assistant is directly put in a developing tank during development. Or, a solid treating agent containing a thioether compd. expressed by A-(R<1> -S)n -R<2> -S-R<3> -B is directly put in a developing tank during development.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material having excellent development stability during long-term running, and particularly having a spectral maximum sensitivity of 600 nm or more. The present invention relates to a method for processing a silver halide photographic material capable of obtaining excellent development processing stability even when development processing is performed with low replenishment.

[0002]

2. Description of the Related Art In 1995, the dumping of developing wastewater into the ocean was banned, and voices of environmental preservation became more and more important. As a result, the amount of developing replenisher used in automatic developing machines was reduced. Is coming.

When the amount of the developing replenisher is reduced, the components eluted from the processed photosensitive material are accumulated in the developing tank, and the components of the developing solution are consumed (the inhibitor is taken out by the photosensitive material, the developing agent and the developing auxiliary agent). Sensimetry becomes unstable, resulting in desensitization and a decrease in Dm. Furthermore, when the replenishment rate is reduced, the residence time of the processing solution is extended, so that oxidative fatigue is advanced and sensitometry is further destabilized.

In order to solve these problems, in a photosensitive material for medical use, means for improving the developability of silver halide grains (for example, selenium sensitization, reduction sensitization, halogen composition / aspect ratio of tabular grains). Increase, decrease binder amount, use new binders, such as dextran and dextrins, and improve the developing solution (eg, use high pH to increase developability, increase developing agent, add development accelerator) ) Has been proposed, but with a photosensitive material having a spectral sensitivity maximum at 600 nm or more, a satisfactory result was not obtained by these techniques.

Therefore, in a development processing system for processing a photosensitive material having a spectral maximum at 600 nm or more, the replenishment amount of the processing solution has to be increased in order to obtain development processing stability. Even if it is supplemented, the effect of restoring stability cannot be obtained sufficiently, and increasing the amount of replenisher not only goes against the direction of environmental conservation, but also increases the frequency of replacement of treatment agent kits. It is not easy to use. In recent years, this problem has become a fatal defect as replenishment progresses.

[0006] Accordingly, there has been a strong demand for a processing method for solving the above-mentioned problems in a light-sensitive material having a spectral maximum at 600 nm or more.

[0007]

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains having a spectral maximum of at least 600 nm on a support. It is an object of the present invention to provide a method of processing a silver halide photographic material which is excellent in long-term development processing stability even when a low replenishment processing is performed in a method of developing a material by adding a development replenisher.

[0008]

The object of the present invention is to provide: (1) a silver halide having at least one silver halide emulsion layer containing silver halide grains having a spectral maximum at 600 nm or more on a support; In the method of developing a photographic light-sensitive material by adding a developing replenisher, the molar ratio of the developing auxiliary to the developing agent in the developing replenisher is the molar ratio of the developing auxiliary to the developing agent in the developing starter. using the developer replenisher is 1.1 times or more, and method for processing a silver halide photographic light-sensitive material characterized in that the the replenishing amount of ^{50ml / m 2 ~200ml / m 2} . (Hereinafter referred to as the first invention) (2) A replenisher for developing a silver halide photographic material having a silver halide emulsion layer containing at least one silver halide grain having a spectral maximum at 600 nm or more on a support. Wherein a solid processing agent containing a developing agent is directly charged into a development processing tank during the development processing. (Hereinafter referred to as the second invention) (3) A developing replenisher for a silver halide photographic material having a silver halide emulsion layer containing at least one silver halide grain having a spectral maximum at 600 nm or more on a support. A method for processing a silver halide photographic material, wherein a solid processing agent containing a development auxiliary agent is directly charged into a development processing tank during the development processing. (Hereinafter referred to as "third invention") (4) A replenisher for developing a silver halide photographic material having at least one silver halide emulsion layer containing silver halide grains having a spectral maximum at 600 nm or more on a support. Wherein a solid processing agent containing a thioether compound represented by the following general formula (1) is directly charged into a development processing tank during the development processing. Processing method of photosensitive material. (Hereinafter referred to as a fourth invention.) General formula (1) A- (R ¹ -S) n-R ² -SR ³ -B wherein R ¹ , R ² and R ³ are an alkylene group or Represents an alkylene group linked by an ether bond. R ¹ ,
R ² and R ³ may form a ring with R ¹ and R ³ or R ² and R ³ . А and B may be the same or different and each represents a hydrogen atom, an alkyl group, an amino group, an ammonium group, a hydroxy group, a carboxy group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group. A and B may form a ring with A and B. n represents an integer of 0 to 10. (5) The replenishment amount of the development replenisher is 50 ml / m ² to 200
The method according to any one of claims 2-4, characterized in that the ml / m ^2. (6) The processing method according to any one of claims 1 to 5, wherein the developing agent of the developer is a reductone. Achieved by

As a result of extensive studies by the present inventors, development replenishment of a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains having a spectral maximum at 600 nm or more on a support is provided. In the method of developing by adding a developing solution, the molar ratio of the developing auxiliary agent to the developing agent in the replenisher ((Developing auxiliary agent) / (Developing agent) [molar ratio]] By making the molar ratio of the main agent [(development auxiliary agent) / (developer agent) [molar ratio]] 1.1 times or more, it was found that excellent long-term development processing stability can be obtained in low replenishment processing. .

When the (development auxiliary agent) / (developer agent) [molar ratio] of the development replenisher is 1.1 times or more of the development start solution, the reason for the low replenishment processing (replenishment amount 50 ml / m ²⁾
~ 200 ml / m ² ), it is not clear whether excellent long-term development processing stability can be obtained.
600 n of the developing agent which is considered to reduce and recover the development auxiliary agent which is super-additive and oxidized by the developing reaction is reduced.
The silver halide photographic light-sensitive material having a spectral maximum not less than m does not work effectively due to processing fatigue due to running and oxidative fatigue due to long-term running, and the development auxiliary agent itself is oxidized and reduced. , The developing stability deteriorates and excellent long-term development processing stability cannot be obtained. However, the amount of the development auxiliary agent to be replenished with the development replenisher is changed to (development auxiliary agent) / (developer agent) [molar ratio] to the development start solution. It is presumed that excellent long-term development processing stability can be obtained by setting the molar ratio of (development auxiliary agent) / (developer agent) to 1.1 times or more.

Also, at least one layer of 600
A method for developing a silver halide photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains having a spectral maximum at or above nm by adding a development replenisher,
During the development processing, a solid processing agent containing a developing agent, a solid processing agent containing a development auxiliary agent, or a solid processing agent containing a thioether compound represented by the above general formula (1) is directly put into a developing tank. It was found that by adding the above, excellent long-term development processing stability was obtained in low replenishment processing.

[0012] It is not yet clear why excellent long-term development processing stability can be obtained in a low replenishment process by directly adding a developing agent or a development auxiliary agent as a solid processing agent to a development processing tank. However, unlike the case where the developing agent or the developing auxiliary agent is used as a solution, for example, the concentration kit is diluted and put into the developing tank, for some reason, the resilience of the developing auxiliary agent by the developing agent increases. It is also presumed that this is because the ability of the developing agent to recover the developing auxiliary agent increases.

[0013] Why is it possible to obtain excellent long-term development processing stability in low replenishment processing by directly charging the thioether compound represented by the above general formula (1) as a solid processing agent into a development processing tank? Although not clear, the thioether compound represented by the general formula (1)
It has the ability to characteristically develop and activate a silver halide photographic material having a silver halide emulsion layer containing silver halide grains having a spectral maximum at 600 nm or more. It is presumed that the ability will be enhanced by being introduced.

The method for processing a silver halide photographic light-sensitive material of the present invention can provide excellent long-term development processing stability even when processing with a small replenishment amount. Further, when reductones are used as a developing agent, the effect becomes remarkable.

Hereinafter, the present invention will be described in detail.

First, the silver halide photographic light-sensitive material used in the present invention will be described.

The silver halide photographic light-sensitive material used in the present invention is a silver halide photographic light-sensitive material having a silver halide emulsion layer having a spectral maximum sensitivity at a wavelength of 600 nm or more.

The silver halide emulsion contains silver halide grains such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloride and silver bromide. It is silver bromide.

The average grain size of the silver halide grains is 0.10 to 0.10.
It is 0.35 μm, preferably 0.10 to 0.25 μm.

The silver halide may be iridium-doped silver halide. The iridium compound can be selected from a single salt or a metal complex.

The silver halide grains may be chemically sensitized with a selenium and / or tellurium compound in the presence of a spectral sensitizing dye described below. A wide variety of selenium and tellurium compounds can be used.

In the present invention, silver halide emulsion grains are spectrally sensitized by a spectral sensitizing dye so as to have a spectral maximum at a wavelength of 600 nm or more. More preferably, it is spectrally sensitized so as to have a spectral maximum in a wavelength range of 600 to 1200 nm, and a wavelength of 600 to 1000 nm.
It is particularly preferable that the light-sensitive material is spectrally sensitized so as to have a spectral maximum in the range.

In the present invention, the spectral sensitizing dye used for spectral sensitization is not particularly limited. For example, 60
As the spectral sensitizing dye that gives spectral maximum sensitivity in the range of 0 to 1200 nm, for example, cyanines such as cyanine, carbocyanine, dicarbocyanine, holopolar cyanine, and complex cyanine, merocyanine, and complex merocyanine can be advantageously used. it can.

Examples of the spectral sensitizing dye which can be preferably used in the present invention include sensitizing dyes represented by the following general formulas [1], [2] and [3], and are selected from these sensitizing dyes. Spectral sensitization can be performed using at least one kind.

[0025]

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In the general formula [1], Z ₁ and Z ₂ each represent a nonmetallic atom group necessary for forming an azole ring which may have a substituent, and R ₁ and R ₂ are Represents an alkyl group or a substituted alkyl group.

X represents an ion necessary to cancel the electric charge of the molecule. n represents the number required to neutralize the total charge of the molecule. However, when an inner salt is formed, 0
It is.

The azole ring formed by Z ₁ and Z ₂ may be the same or different.

Examples of the azole ring include a benzothiazole ring (for example, a benzothiazole ring, a 5-chlorobenzothiazole ring, a 5-methylbenzothiazole ring, a 5-methoxybenzothiazole ring, a 5-hydroxybenzothiazole ring). Ring, 5-hydroxy-6-methylbenzothiazole ring, 5,6-dimethylbenzothiazole ring, 5-ethoxy-6-methylbenzothiazole ring,
-Phenylbenzothiazole ring, 5-carboxybenzothiazole ring, 5-ethoxycarbonylbenzothiazole ring, 5,6-dimethylaminobenzothiazole ring,
-Acetylaminobenzothiazole ring, etc., benzoselenazole ring (for example, benzoselenazole ring, 5-chlorobenzoselenazole ring, 5-methylbenzoselenazole ring, 5-methoxybenzoselenazole ring, 5-hydroxybenzoselena Zole ring, 5,6-dimethylbenzoselenazole ring, 5,6-dimethoxybenzoselenazole ring, 5-ethoxy-6-methylbenzoselenazole ring, 5-hydroxy-6-methylbenzoselenazole ring, 5-phenyl Benzoselenazole ring, etc.), naphthothiazole ring (for example, β-naphthothiazole ring, β,
β′-naphthothiazole ring) and naphthoselenazole ring (eg, β-naphthoselenazole ring).

Examples of the alkyl group or substituted alkyl group represented by R ₁ and R ₂ include alkyl groups such as methyl, ethyl and n-propyl, β-carboxyethyl, γ-carboxypropyl, γ And substituted alkyl groups such as -sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, and sulfoethoxyethyl group.

Examples of ions necessary to cancel the electric charge of the molecule represented by X include halogen ions and
Examples include perchlorate ion, thiocyanate ion, benzenesulfonate ion, p-toluenesulfonate ion, and methylsulfate ion.

[0032]

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In the general formula [2], Z ₃ and Z ₅ are non-metallic atomic groups necessary for forming a benzothiazole, naphthothiazole, benzoxazole or naphthoxazole ring which may have a substituent. Represents Z ₄ represents a non-metallic atomic group necessary for forming a 5- or 6-membered carbon atom ring which may have a substituent, and R ₃ and R ₄ represent an alkyl group or a substituted alkyl group, respectively. Represents

X represents an ion necessary to cancel the electric charge of the molecule. n represents the number required to neutralize the total charge of the molecule. However, when an inner salt is formed, 0
It is.

The benzothiazole ring, naphthothiazole ring, benzoxazole ring and naphthoxazole ring formed by Z ₃ and Z ₅ include, for example, benzothiazole ring, [1,2d] naphthothiazole ring, [2, 1d]
Naphthothiazole ring, [2,3d] naphthothiazole ring, benzoxazole ring, [1,2d] naphthooxazole ring, [2,1d] naphthoxazole ring, [2,3]
3d] naphthoxazole ring). Examples of the substituent include an alkyl group having 1 to 4 carbon atoms and 1 carbon atom.
To 4 alkoxy groups, phenyl groups or halogen atoms (eg, chloro and bromo atoms).

As the alkyl group or substituted alkyl group represented by R ₃ and R ₄ , for example, an alkyl group having 1 to 4 carbon atoms which may have a substituent (for example, a methyl group, an ethyl group, Hydroxyethyl group, 2-methoxyethyl group,
2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, vinylmethyl group, benzyl group Phenethyl group, p-sulfophenethyl group, n-
Propyl group, isopropyl group, n-butyl group, etc.).

X and n have the same meanings as X and n in the general formula [1].

In the sensitizing dye represented by the general formula [2], the 5- or 6-membered carbon atom ring which may be substituted by Z ₄ may have a substituent. Examples of the 5-membered carbon atom ring include, for example, the following general formula [2-
The sensitizing dye represented by a) can be mentioned.

[0039]

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In the general formula [2-a], R ₈ and R _{9 each} represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, chlorine atom, bromo Atoms and an aryl group as R ₁₀ and R ₁₁ , an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent (for example, a phenyl group, an m-tolyl group,
m-chlorophenyl group, p-chlorophenyl group, alkoxy group having 1 to 4 carbon atoms substituted, for example, p-methoxyphenyl group and the like, alkoxycarbonylalkyl group having 1 to 4 carbon atoms (for example, ethoxycarbonylmethyl group and the like) ) Represents, as R ₁₂ , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, and a phenyl group.

[0041] _{Z 3, Z 5, R 3} , R 4, X and n have the same meanings as _{Z 3, Z 5, R 3} , R 4, X and n in the general formula (2).

In the sensitizing dye represented by the general formula [2], the 5- or 6-membered carbon atom ring which may be substituted by Z ₄ may have a substituent. Examples of the 6-membered carbon atom ring include, for example, the following general formula [2-
sensitizing dyes represented by b).

[0043]

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In the general formula [2-b], R ₁₃ and R ₁₄
Examples thereof include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a phenyl group.

[0045] _{Z 3, Z 5, R 3} , R 4, X and n have the same meanings as _{Z 3, Z 5, R 3} , R 4, X and n in the general formula (2).

[0046]

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In the general formula [3], Z ₆ represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may have a substituent, and R ₅ and R ₆ Represents an alkyl group or a substituted alkyl group, R ₇ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group, and Y represents a hydrogen atom or a substituent.

M and p represent 1 or 2.

X and n have the same meanings as X and n in the general formula [1].

Examples of the 5- to 6-membered nitrogen-containing heterocyclic ring formed by Z ₆ include a thiazole ring, a selenazole ring, an oxazole ring, a 3,3-alkylindolenin ring, and an imidazole ring.

Among these, preferred 5- to 6-membered nitrogen-containing heterocycles are, for example, a thiazole ring (preferably a benzothiazole ring or a naphthothiazole ring) and an oxazole ring (a benzoxazole ring or a naphthoxazole ring). ).

As the alkyl group represented by R ₅ and R ₆ , an alkyl group having 1 to 8 carbon atoms is preferable. Examples of the substituent of these alkyl groups include a carboxyl group, a sulfone group, a cyano group, a halogen atom (eg, a chlorine atom, a bromo atom, a fluorine atom, etc.), a hydroxyl group,
An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 8 or less carbon atoms), an alkoxy group (preferably an alkoxy group having 7 or less carbon atoms), an aryloxy group, an acyloxy group (preferably an acyloxy group having 3 or less carbon atoms) , An acyl group (preferably an acyl group having 8 or less carbon atoms), a carbamoyl group, a sulfamoyl group, and an aryl group.

As R ₇ , an alkyl group having 1 to 4 carbon atoms, a benzyl group and the like are preferable.

The substituent represented by Y is, for example,
Examples thereof include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, and a halogen atom. The alkyl group may have a substituent. Examples of the substituent include a carboxymethyl group, a trifluoromethyl group, and an alkoxy group. Is mentioned.

P represents 1 or 2, and when p is 2, each Y may be the same or different.

Next, specific examples of the sensitizing dyes represented by the general formulas [1], [2] and [3] are shown, but the spectral sensitizing dyes used in the present invention are not limited to these. Absent.

[0057]

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[0058]

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[0059]

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As the sensitizing dye represented by the general formula [1], dyes represented by specific examples (1) to (32) described in JP-A-3-200953 can be further exemplified.

Further, as the sensitizing dye represented by the general formula [2], the dyes represented by 1-1 to 1-16 of the general formula [1] described in JP-A-4-251839 can be further used. Can be mentioned.

The sensitizing dye represented by the general formula [3] further includes 2-1 to 2- of the general formula [2] described in the same publication.
The dye represented by 10 can be mentioned.

The sensitizing dyes represented by the general formulas [1], [2] and [3] are described, for example, in "The Chemis" by FM Hamer.
The compound can be synthesized by the method described in "try of Heterocyclic Compound" Vol. 18 or a method analogous thereto.

The spectral sensitizing dye is preferably used in the range of 0.003 g to 0.3 g, more preferably 0.005 g to 0.15 g, per mole of silver halide.

These sensitizing dyes may be added directly to the silver halide emulsion, but may be added to a suitable hydrophilic solvent, for example,
It may be added by dissolving in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water or a mixed solution thereof. An ultrasonic method can be used for dissolution in a hydrophilic solvent.

These sensitizing dyes are described in, for example, US Pat. Nos. 3,469,987 and 3,822.
No. 135, JP-B-46-24185, JP-A-50-80826, and JP-A-51-74624.

The spectral sensitizing dye may be added to the silver halide emulsion during the silver halide grain production process, after production, before or after desalination, before chemical sensitization, during chemical sensitization, or after chemical sensitization. Can be added, but preferably before or during chemical sensitization.

Next, the developing agent and the auxiliary developing agent used in the method for processing a silver halide photographic light-sensitive material of the present invention will be described.

In the present invention, the developing agent and the developing auxiliary agent may be used alone or in combination of two or more.

In the present invention, it is preferable to use reductones as a developing agent. Further, as the reductone, a reductone represented by the following general formula (II) is preferable.

[0071]

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In the general formula (II), R ₂₁ and R ₂₂ are
These represent a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, and an alkylthio group, respectively.

X ₁₁ represents an atomic group necessary for forming a 5- or 6-membered ring.

The amino group represented by R ₂₁ and R ₂₂ includes, for example, an amino group such as an ethyl group, a butyl group,
A hydroxyethyl group, an amino group substituted with an alkyl group having 1 to 10 carbon atoms, and the like, as the acylamino group, for example, an acetylamino group, a benzoylamino group, and as the alkylsulfonylamino group, for example, Examples include a methanesulfonylamino group, examples of the arylsulfonylamino group include a benzenesulfonylamino group and a p-toluenesulfonylamino group, and examples of the alkoxycarbonylamino group include a methoxycarbonylamino group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

As R ₂₁ and R ₂₂ , a hydroxyl group,
Preferred are an amino group, an alkylsulfonylamino group, an arylsulfonylamino group, and the like.

The group of atoms necessary for forming the 5- to 6-membered ring represented by X ₁₁ is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom.

The atomic group necessary for forming the 5- to 6-membered ring represented by X ₁₁ includes, for example, —O—, —C (R ₂₃ )
_{(R 24) -, - C} (R 25) =, - C (= O) -, - N
_{(R 26) -, - N} = the combined atomic group and the like. Here, R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (for example, a hydroxyl group, a carboxyl group, a sulfo group) A hydroxyl group and a carboxyl group.

The 5- to 6-membered ring formed by X ₁₁ may have a saturated or saturated condensed ring.

The 5- or 6-membered ring formed by X ₁₁ includes, for example, dihydrofuranone, dihydropyrone, pyranone,
Each ring includes cyclopentenone, pyrrolinone, pyrazolinone, pyridone, azacyclohexenone, uracil and the like. Preferred 5- to 6-membered rings are dihydrofuranone, cyclopentenone, cyclohexanone, pyrazolinone, azacyclohexenone, and uracil.

The compound represented by the general formula (II) may be a salt such as lithium, sodium, potassium, and ammonium.

Specific examples of the reductone represented by the general formula (II) are shown below, but the reductones that can be used in the present invention are not limited thereto.

[0082]

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[0083]

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[0084]

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As the reductone used in the developer of the present invention, ascorbic acid or erythorbic acid (stereoisomer) (II-1) is preferable.

In the developing solution of the present invention, the reductone is preferably used in an amount of 1 to 100 g, more preferably 5 to 50 g per liter of the developing solution.

As the developing agents, the following developing agents can be used in addition to the reductones.

The developing agents that can be used include dihydroxybenzenes (hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, i-propylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethyl Hydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate) and aminophenols.

The developing auxiliary agent is a developing agent which exhibits superadditivity when used together with the developing agent.

The development aids which can be used in the present invention include 3-pyrazolidones [1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl- 3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2 -Benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone and the like]; aminophenols (o-
Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.); 1-allyl-3-aminopyrazolines [1- (p -Hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-aminopyrazoline, etc.]; pyrazolones (Such as 4-aminopyrazolone) or a mixture thereof.

Among these, preferred development auxiliary agents are 1-phenyl-3-pyrazolidones.

In the present invention, as the combination of the developing agent and the developing auxiliary agent, a combination of the developing agent and the developing auxiliary agent which is superadditive in the development theory is selected.

Preferred combinations are 1-phenyl-3-pyrazolidone / erythorbic acid, 1-phenyl-3-pyrazolidone /
Hydroquinone, dimazone S / erythorbic acid or hydroquinone, dimazone / erythorbic acid or hydroquinone. More preferred is a combination of 1-phenyl-3-pyrazolidone / erythorbic acid and dimezone S / erythorbic acid.

The development start solution is different from the development replenisher.
[(Developing auxiliary agent) / (Developing agent) specified in the first invention
[Molar ratio]] may be injected into the developing tank using a start kit adjusted so that the developing replenisher is injected into the developing tank, a starter is added, and the developing tank is filled. In this state, it may be adjusted so as to obtain [(development auxiliary agent) / (development agent) [molar ratio]] defined in the first invention.

In the developing solution, in addition to the development auxiliary agent and the developing agent, if necessary, a preservative (sulfite, bisulfite, etc.) and a buffer (carbonate, borate, borate, alkanolamine) ), Alkaline agents (such as carbonates), dissolution aids (such as polyethylene glycols and esters thereof), p
H adjusters (organic acids such as citric acid and tartaric acid), sensitizers (quaternary ammonium salts, etc.), development accelerators, hardeners (dialdehydes such as glutaraldehyde), surfactants, etc. be able to. Further, antifoggants such as azole organic antifoggants (indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole, thiadiazole) and the like, for covering calcium ions mixed in tap water. A concealing agent (sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, etc.) may be added. Further, as a silver stain preventing agent, for example,
The compounds described in JP 24347 can be used.

The pH of the developer used in the method for processing a silver halide photographic light-sensitive material of the present invention is preferably in the range of 9 to 12, more preferably 9.5 to 10.5.

Further, in the developer, JP-A-56-1062 was used.
Amino compounds such as alkanolamines described in JP-B-44 can be used. In addition, L. F. A. Mason, Photographic Processing Chemistry, Focal Press (1966) 22-
229, U.S. Pat. Nos. 2,193,015 and 2,592,364, JP-A-48-6493.
You may use the additive described in No. 3 publication.

The developing solution and the developing replenisher used in the present invention are:
It is preferable to prepare a solid developer and dissolve and supply the solid developer for storage stability.

When the developer is solidified, it is preferable that all of the alkali agent and the reducing agent are used as a solid processing agent, and in the case of tablets, it is preferable that at least three agents are used, most preferably one agent is used. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged together.

Further, when granulating, it is preferable that the above effect is further remarkable by granulating each component, for example, in the case of a developer by dividing into an alkali agent, a reducing agent, a preservative and the like.

When replenishing the developing replenisher, a solid developer may be directly added to the developing tank together with water.

The replenishment of the developing replenisher is controlled and supplied by a control means for supplying a fixed amount of a solid processing agent according to the processing amount information of the photosensitive material. In an automatic processor, it is necessary to keep the concentration of components in each processing tank constant and to stabilize photographic performance. The processing amount information of the photosensitive material is a value proportional to the processing amount of the photosensitive material processed with the processing solution, the processing amount of the processed photosensitive material or the processing amount of the photographic photosensitive material being processed. This is information indicating indirectly or directly the amount of decrease in the treatment agent. This information may be detected at any timing before or after the photosensitive material is carried into the processing solution or during immersion in the processing solution. Further, physical parameters such as the concentration of the composition in the processing solution, a change in the concentration, pH, and specific gravity may be used. Alternatively, the amount of the treatment liquid that has come out after drying may be used. In addition, the supply of the development replenisher is stopped
It is obtained by detecting information that a predetermined amount of supply has been completed.

In the first invention, the (molar ratio) of (development auxiliary agent) / (developer agent) of the developing replenisher is 1 to (molar ratio) of (development auxiliary agent) / (developer agent) of the development start solution. The value is 1 or more times, but preferably 1.1 to 3.0 times. Although the effect of the present invention can be obtained at 3.0 times or more,
It is not preferable because fog is deteriorated.

In the second invention, a solid processing agent containing a developing agent is used. In the third invention, a solid processing agent containing a development auxiliary agent is used. In the fourth invention, a solid processing agent containing a developing agent is represented by the following general formula (I). The solid processing agent containing the thioether compound is directly charged into the developing tank. General formula (I) A- (R ¹ -S) n-R ² -SR ³ -B [wherein R ¹ , R ² and R ³ represent an alkylene group or an alkylene group linked by an ether bond. . R ¹ ,
R ² and R ³ may form a ring with R ¹ and R ³ or R ² and R ³ . А and B may be the same or different and each represents a hydrogen atom, an alkyl group, an amino group, an ammonium group, a hydroxy group, a carboxy group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group. A and B may form a ring with A and B. n represents an integer of 0 to 10. Next, the solid processing agent containing the developing agent, the solid processing agent containing the development auxiliary agent, and the solid processing agent containing the thioether compound represented by the general formula (I) will be described.

The term "solid processing agent" as used herein means a processing agent which is in a solid state such as a tablet processing agent, a granulation processing agent, and a powder processing agent.

As the developing agent and the developing auxiliary in the solid processing agent containing the developing agent and the solid processing agent containing the developing auxiliary, the developing agent and the developing auxiliary described above can be used.

The solid processing agent containing the thioether compound represented by the above general formula (I) used in the fourth invention is used. In the general formula (I), R ¹ , R ²
And the alkylene group represented by R ³ has 1 carbon atom
An alkylene group having 10 to 10 is preferable, and an alkylene group having 1 to 6 carbon atoms is particularly preferable.

Examples of the alkylene group or the alkylene group linked by an ether bond include -CH ₂ CH ₂ -,-
_{(CH 2) 3 -, -} (CH 2) 4 -, - (CH 2) 2 -O-
_{(CH 2) 2 -, -} CH 2 -CH (OH) -CH 2 - and the like.

The alkyl groups represented by A and B include:
An alkyl group having 1 to 10 carbon atoms (including those having a substituent) is preferable. Examples thereof include a methyl group and an ethyl group. Examples of the amino group (including those having a substituent) include dimethyl. Amino group, diethylamino group,-
_{N (CH 2 CH 2 CN)} 2, -N (CH 2 -CH (OH) -
CH ₂ OH) ₂ , —NH ₂ and morpholino groups.
Examples of the ammonio group (including those having a substituent) include a trimethylammonio group, and examples of the aminocarbonyl group (including those having a substituent) include a dimethylaminocarbonyl group. ,
Examples of the aminosulfonyl group (including those having a substituent) include a dimethylaminosulfonyl group. As A and B, among these, a hydrogen atom, an amino group, and an ammonium group are preferable.

The compound represented by the formula (I) may be in the form of a salt with an inorganic or organic acid. Preferred examples of the inorganic or organic acid include hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid. , Hydroiodic acid, perchloric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like.

The specific examples of the compounds represented by formula (I) are shown below, but the present invention is not limited only to these compounds.

[0112]

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[0113]

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[0114]

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The compound represented by the general formula (I) or a salt thereof can be synthesized by an ordinary method.

Solid processing agents containing a developing agent include, in addition to the developing agent, solid processing agents containing a developing auxiliary agent include, in addition to the developing agent, a thioether compound represented by the general formula (I). In addition to the thioether compound represented by the general formula (I), if necessary, a preservative (sulfite, bisulfite, etc.) and a buffer (carbonate, borate, Borate, alkanolamine, etc.), alkaline agent (carbonate, etc.), dissolution aid (polyethylene glycols,
, PH adjusters (organic acids such as citric acid and tartaric acid), sensitizers (quaternary ammonium salts, etc.), development accelerators, hardeners (dialdehydes such as glutaraldehyde), A surfactant or the like can be contained. Further, azole organic antifoggants (indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole,
An antifoggant such as thiadiazole) and a masking agent (sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, etc.) for masking calcium ions mixed in tap water may be added. As the silver stain inhibitor, for example, the compounds described in JP-A-56-24347 can be used.

Further, a binder can be used for forming the solid processing agent. As a binder that can be used,
The saccharides (monosaccharides, polysaccharides in which a plurality of monosaccharides are glycosidically bonded to each other, and their decomposed products) described in Japanese Patent Application No. 6-91987 (pages 23 to 30) are preferred.
Those selected from dextrins and sugar alcohols are particularly preferred, and have little change in shape even when stored for a long period of time.

Further, in the solid processing agent, it is preferable to use acylated amino acids described in Japanese Patent Application No. 5-186254 (pages 9 to 15) as a lubricant. The solid processing agent can be manufactured stably without impairing the strength, the solubility is less deteriorated, and the storage stability and dust generation are improved.

To the solid processing agent, a hydroxylamine, phenylcarboxylic acid, phenylsulfonic acid, hydroxyl group or carboxyl group described in Japanese Patent Application No. 6-70860 (pages 14 to 33) is introduced as a coating agent. It is preferable to use alkyl (or alkenyl) carboxylic acids, sulfites, water-soluble polymers (polyalkylene glycol, methacrylic acid type betaine type polymer, etc.), and saccharides. The generation of fine powder is small, the deterioration of solubility is small, and excellent storability can be maintained and stable photographic performance can be maintained.

In the present invention, the solid processing agent containing a developing agent is preferably a solid processing agent in which 95% or more of the components excluding the binder are the developing agent. Solid processing agents in which 95% or more of the components excluding the agent are development auxiliary agents are preferable, and solid processing agents containing a thioether compound represented by the general formula (I) include:
Solid processing agents in which 99% or more of the components excluding the binder are thioether compounds represented by the general formula (I) are preferred.
Further, a preservative or the like may be partially contained.

The above-mentioned solid processing agent is formed, for example, by kneading the concentrated liquid or fine powder or granules with a water-soluble binder and molding, or spraying the water-soluble binder on the surface of the temporarily molded fixing agent. It can be formed by any means such as forming a coating layer by using a method. Regarding the formation of solid processing agents,
JP-A-4-29136, JP-A-4-85535, JP-A-4-85536, JP-A-4-85533, JP-A-4-85534, and JP-A-4-172341 can be referred to. it can.

In the present invention, the solid processing agent preferably has a tablet shape. A preferred tablet production method is a method of granulating a powdered treatment agent and then tableting to form a tablet. According to this manufacturing method, solubility and storage stability are improved compared to a solid processing agent obtained by simply mixing a solid component and tableting to form a tablet, and as a result, photographic performance is also stable. There is an advantage of becoming.

Granulation methods include rolling granulation, extrusion granulation,
Known methods such as compression granulation, crushing granulation, stirred granulation, fluidized bed granulation, and spray drying granulation can be used.

The average particle size of the granulated product should be 100 to 800 μm when mixing and compressing the granulated product to form a tablet, because the components are not made uniform, so-called segregation is unlikely to occur. Is more preferable, and more preferably 200 to 750 μm.
m. The particle size distribution of the granulated product is preferably such that 60% or more of the granulated product particles have a deviation of ± 100 to 150 μm.

For compressing the obtained granules under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a briquetting machine can be used. . The solid processing agent obtained by pressurizing and compression can take any shape.However, from the viewpoint of productivity and handling, and from the problem of dust when used on the user side, a cylindrical type agent is used. So-called tablets are preferred.

Tablet processing agents are described, for example, in JP-A-51-61.
Nos. 837 and 54-155038 and 52-
No. 88025, British Patent 1,213,808, etc., and can be produced by a general method. Granulating agents are described in, for example, JP-A-2-10942 and 2-1.
09043, JP-A-3-39735 and JP-A-3-39735
For example, the powder processing agent can be produced by a general method described in JP-A-39339 or the like.
Gazette, British Patent Nos. 725,892 and 729,
It can be produced by a general method described in, for example, 862 and German Patent 3,733,861.

When the bulk density of the solid processing agent is a tablet,
From the viewpoint of its solubility and the achievement of the object of the present invention, 1.0 to 1.0
2.5 g / cm ³ is preferred. Bulk density is 1.0 g / cm ³
If it is smaller, sufficient strength cannot be obtained, and 2.5 g / cm ³
Larger and sufficient solubility cannot be obtained. When the solid processing agent is granules or powder, the bulk density is 0.40.
0.95 g / cm < ³ > is preferable.

As the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783, Japanese Unexamined Patent Application Publication No. 63-97522, Japanese Unexamined Utility Model Publication No. A publicly known method described in a gazette or the like may be used, but any method may be used as long as the function of supplying a tablet to a processing tank is provided at a minimum. Also,
When the solid processing agent is granules or powders,
Nos. 819964, 63-84151, and Japanese Patent Application Laid-Open No. 1-292375, etc., and a gravity drop method described in JP-A-63-105159 and 63-195345.
Nos. 6,098,089 and 6,098,086, and the like, but are not limited thereto.

As a preferable supply means for replenishing and supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent is weighed in advance and divided and packaged, and the package is packed according to the processing amount of the photosensitive material. A method of opening, taking out and supplying can be considered. Specifically, the solid processing agent is sandwiched and stored in a predetermined amount, preferably in a single replenishment amount, in a package composed of at least two packaging materials, and the package is separated in two directions or the package is separated. Is opened so that it can be taken out, and the solid processing agent is supplied by gravity to a processing tank having a filtering means. When the solid processing agent is housed in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is shut off, moisture resistance until opening can be obtained.

The packaging form of the solid processing agent is such that a package made of at least two packaging materials sandwiching the solid processing agent is in close contact with each other so that the periphery of the solid processing agent can be separated. An adhesive configuration is conceivable. With the solid processing agent packaged in the above configuration, the contact surface adhered or adhered is separated by pulling each packaging material sandwiching the solid processing agent in a different direction, and the solid processing agent can be taken out. it can. In addition, in a package made of at least two packaging materials configured to sandwich the solid processing agent, a configuration in which at least one end can be opened by an external force may be considered. The term “openable” as used herein means that a part of the packaging material is cut or broken so that it can be easily opened by external force. As the opening method, the solid processing agent is forcibly pushed out by applying a compressive force from the non-opening side package to the openable package via the solid processing agent, or the openable side package is opened. It is conceivable that the solid processing agent can be taken out by making a cut in the body with a sharp member.

The supply of the solid processing agent containing the developing agent, the solid processing agent containing the developing auxiliary agent, and the solid processing agent containing the thioether compound is started by detecting the information on the processing amount. The supply can be started by a signal, and the supply can be stopped by a supply stop signal output by detecting information that a predetermined amount of the supply has been completed.

When the solid processing agent is packaged, it is possible to control the drive means for separating or opening based on the supply start signal and stop the drive means for separating or opening based on the supply stop signal. .

The solid processing agent is supplied under the control of a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the photosensitive material. In an automatic processor, it is necessary to keep the concentration of components in each processing tank constant and to stabilize photographic performance. The processing amount information of the photosensitive material is a value proportional to the processing amount of the photosensitive material processed with the processing solution, the processing amount of the processed photosensitive material or the processing amount of the photographic photosensitive material being processed. This is information indicating indirectly or directly the amount of decrease in the treatment agent. This information may be detected at any timing before or after the photosensitive material is carried into the processing solution or during immersion in the processing solution. Further, physical parameters such as the concentration of the composition in the processing solution, a change in the concentration, pH, and specific gravity may be used. Alternatively, the amount of the treatment liquid that has come out after drying may be used.

The place where the solid processing agent is charged may be in the developing tank, but is preferably a place where the processing liquid is in communication with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. In addition, it is preferable that there is a constant circulation amount of the processing liquid between the processing unit and the processing unit, so that the dissolved components move to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

In an automatic developing machine, the temperature of a processing solution is controlled by an electric heater. Generally, in order to control the temperature of the processing liquid, a heat exchange unit is provided in an auxiliary tank connected to the processing tank, a heater is installed, and a pump is installed in this auxiliary tank so that the liquid can be sent from the processing tank at a constant circulation rate. Is arranged. At the outlet of the auxiliary tank, a filter is arranged so that insoluble portions such as crystal foreign substances mixed in the processing liquid or generated by crystallization can be removed.

The most preferable method is to put a solid processing agent into a place where the temperature is controlled, such as a place communicating with the processing section, such as the auxiliary tank. This is because the insoluble components of the input processing agent are blocked by the filter unit, solids can be prevented from flowing into the processing unit and adhering to photosensitive materials, etc., and the solid processing agent has very good solubility. Becomes

[0137] The processing tank may be provided with a processing agent charging section together with the processing section. In this case, it is preferable to take measures such as shielding in the processing solution or shielding the insoluble portion such as crystalline foreign matter generated by crystallization from directly contacting the film or the like being processed.

The frequency of circulation of the processing solution circulating between the processing tank and the auxiliary tank is preferably 0.5 to 2.0 times / min, particularly 0.8 to 2.0 times / min, and more preferably 1 to 2.0 times / min. .0
2.0 times / min is preferable. As a result, the dissolution of the solid processing agent can be promoted, the occurrence of a portion present at a high concentration in the processing agent can be prevented, and the occurrence of density unevenness in the processed photosensitive material can be prevented. In addition, it is possible to prevent the occurrence of insufficiently processed photosensitive material. Here, the number of circulations indicates the amount of the processing solution circulated, and the time when the amount of the liquid corresponding to the total amount of the liquid in the processing tank flows is defined as one time.

The solid processing agent is added to each processing tank separately from the replenishing water. Replenishment water is supplied from the refill tank.

The solid processing agent is preferably added in an amount of 10% to 50% of the replenisher as a developing agent in a solid processing agent containing a developing agent.
In a solid processing agent containing a development auxiliary agent, it is preferable to add an amount of 10% to 100% based on a replenisher as a development auxiliary agent, and contains a thioether compound represented by the general formula (I). In solid processing agents,
It is preferable to add an amount of 1.0 × 10 ^{−2 to} 1.0 × 10 ⁻⁴ mol / L according to the amount of the replenisher.

The addition timing of the solid processing agent is determined by the processing amount of the silver halide photographic material per day, the replenishing amount, and the running time, and the concentration starts to decrease while checking the stability of the processing solution by the concentration. It is preferable to adjust the amount of addition depending on the width of concentration drop at the beginning of addition.

Next, the fixing solution used in the method for processing a silver halide photographic light-sensitive material of the present invention will be described.

The fixing solution used in the present invention is not particularly limited, and various fixing solutions can be used, but it is preferable to prepare from a solid fixing agent prepared in advance.

The fixing agent preferably used in the present invention will be described below.

The fixing agent of the fixing agent preferably contains a thiosulfate. Thiosulfates are usually lithium,
It is used as a potassium, sodium or ammonium salt, but sodium thiosulfate and ammonium thiosulfate are preferred. More preferably, it is ammonium thiosulfate.

Ammonium thiosulfate is preferable since a fixing solution having a high fixing speed can be obtained, but sodium thiosulfate is preferable from the viewpoint of storage stability and the like.

The concentration of the thiosulfate in the fixing solution is preferably from 0.1 to 5 mol / l, more preferably from 0.5 to 2 mol / l, and further preferably from 0.1 to 2 mol / l.
It is 7 to 1.8 mol / liter.

In addition, iodide salts, thiocyanates and the like can be used as fixing agents.

The fixing agent may contain a sulfite. As the sulfite, a solid lithium, potassium, sodium, ammonium salt or the like is used. The concentration of sulfite in the fixing solution is 0.2 mol / liter or less when thiosulfate and sulfite are dissolved and mixed in an aqueous solvent.

The fixing agent may contain a water-soluble chromium salt or a water-soluble aluminum salt. Examples of the water-soluble chromium salt that can be used include chrome Meiwa, and examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride. These water-soluble chromium salts or water-soluble aluminum salts are used in an amount of 0.2 to 3.0 per liter of the fixing solution.
g, preferably 1.2 to 2.5 g.

The fixing agent includes acetate, citrate,
Tartrate, malate, succinate, phenylacetate, and optical isomers thereof may be included. Preferred specific examples of these salts include, for example, potassium citrate,
Lithium citrate, sodium citrate, ammonium citrate, lithium bitartrate, potassium bitartrate,
Lithium, potassium, sodium, ammonium salts represented by potassium tartrate, sodium bitartrate, sodium tartrate, ammonium bitartrate, ammonium potassium tartrate, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc. And the like.

Among the above compounds, more preferred are:
Acetate, citrate, isocitrate, malate and phenylacetate. The amount of these compounds added to the fixing solution is preferably 0.2 to 0.6 mol / liter.

The fixing agent may contain an acid and a salt thereof, a chelating agent, a surfactant, a wetting agent, and a fixing accelerator.

Examples of these acids include sulfuric acid, hydrochloric acid,
Inorganic acids such as nitric acid and boric acid, formic acid, propionic acid,
Examples thereof include organic acids such as acid and malic acid, and preferred are acids such as boric acid and aminopolycarboxylic acids.
Particularly preferred aminocarboxylic acids are β-alanine, piperidic acid and the like. The preferred amount of acid added is
It is 0.5 to 40 g / liter.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. Activators and the like.

Examples of the wetting agent include alkanolamine and alkylene glycol.

As the fixing accelerator, for example, those described in
Thiourea derivatives described in JP-A-35754, JP-B-58-122535 and JP-B-58-122536, alcohols having a triple bond in the molecule, thioethers described in U.S. Pat. No. 4,126,459, etc. Is mentioned.

The pH after dissolution or dilution of the fixing agent is usually 3.8 or more, preferably 4.2 to 5.5.

The fixing agent used in the present invention is preferably a "solid fixing agent exhibiting acidity after dissolution". The “solid fixing agent that shows acidity after dissolution” refers to a solid fixing agent having a pH of less than 7 after being dissolved in water and having a fixing ability. When the solid fixing agent is in the form of a tablet, the solid fixing agent may be prepared separately from the tablet of the main fixing agent and the tablet of the acid agent.

[0161]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 (Preparation of emulsion EM-1) Temperature 60 ° C., pAg 8.0, p
The average grain size was 0.13 μm and the silver iodide content was 2 mol% by controlling the H.sub.2.0 to a double jet method.
To obtain a monodispersed cubic seed emulsion comprising silver iodobromide. Observation by an electron microscope photograph revealed that the twinning rate of this emulsion was 1% or less in number.

Next, this seed emulsion was dispersed in 8.5 liter of a solution containing protective gelatin and ammonia kept at 40 ° C., and the pH was adjusted with acetic acid.

This solution was used as a mother liquor to adjust the pH to 8.0 and the pAg
Was maintained at 8.5, and a 3.2 N aqueous ammoniacal silver nitrate solution and potassium hexachloroiridium (IV) were added to Ag1
An aqueous potassium bromide solution containing 1 × 10 ⁻⁶ mol per mol was added by a double jet method to grow the mixture.

Thereafter, an aqueous potassium bromide solution was sprayed onto the
Over a period of minutes, the pAg was raised to 9.7, and the mixing was terminated 10 minutes after the completion of the addition of the aqueous potassium bromide solution.

The obtained emulsion had an average particle size of 0.24 μm.
This was a tetrahedral monodispersed emulsion having rounded vertices.
The average silver iodide content of the whole grains was 0.2 mol%.

Next, the emulsion was kept at 40 ° C., and a formaldehyde condensate of sodium naphthalenesulfonate and magnesium sulfate were added. The mixture was allowed to stand with stirring, excess salts were removed by decantation, desalting was performed, and gelatin was added. Dispersed.

Next, the obtained emulsion was heated to 55 ° C., and the exemplified sensitizing dye 1-5 was added at 140 m / mol of silver halide.
g was added. Then, an appropriate amount of triphenylphosphine selenide was added.

Further, an appropriate amount of ammonium thiocyanate, chloroauric acid and sodium thiosulfate was added for chemical sensitization.

When the maximum sensitivity was reached, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added for stabilization to prepare emulsion EM-1. (Preparation of Dye Emulsion Dispersion) A dye solution prepared by dissolving 10 kg of the following dye in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate at 55 ° C., and an anionic surfactant (AS) shown below. 110 liters of a 9.3% gelatin solution containing 35 kg was placed in a dispersion kettle and dispersed while maintaining the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the mixture was made up to 240 kg with water.

[0170]

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Using the emulsion EM-1 and the dye emulsified dispersion prepared as described above, a coating solution for the lower layer of the backing layer, a coating solution for the upper layer of the backing layer, a coating solution for the red-sensitive silver halide emulsion layer and a protective layer A coating solution was prepared. <Backing layer lower layer coating solution> Gelatin 400 g i-amyl-n-decylsulfosuccinate sodium salt 0.4 g Antihalation dye 10 g Potassium polystyrene sulfonate (average molecular weight 150,000) 50 g Diethylene glycol 5 g Glyoxal 2 g Dye emulsified dispersion 33 g SMP 4 g

[0172]

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Make up to 7 liters with water.

The antihalation dye and SMP are shown below.

[0175]

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<Coating solution for the upper layer of the backing layer> Gelatin 400 g i-Amyl-n-decylsulfosuccinate sodium salt 10 g Antihalation dye 10 g Polymethyl methacrylate (average particle size: 6 μm) 12 g SAM-1 3 g C ₈ F ₁₇ SO ₃ K 0.3g Griokizal 13.6g Make up to 7 liters with water.

SAM-1 is shown below.

[0178]

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<Red-Sensitive Silver Halide Emulsion Layer Coating Solution> The following components were added to Emulsion EM-1 in the following amounts per mole of silver halide.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1, 1-dimethylol-1-bromo-nitromethane 10 mg potassium polystyrene sulfonate (average molecular weight 150,000) 10 g

[0181]

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<Protective Layer Coating Solution> The following addition amounts are per 1 m ² of the film.

Lime-treated inert gelatin 0.8 g i-amyl-n-decylsulfosuccinate sodium salt 27 mg polymethyl methacrylate (matting agent having an area average particle diameter of 3 μm) 28 mg silicon dioxide particles (area average particle diameter 1.2 μm) 10 mg Ludox AM (colloidal silica (manufactured by DuPont)) 50 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (2% aqueous solution) 5 mg formalin (35%) 10 mg glyoxal (40%) 40 mg Topside 300 (manufactured by Permchem Asia Ltd) 1 mg SAM-1 20 mg C ₈ F ₁₇ SO ₃ K 2 mg

[0184]

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<< Preparation of Silver Halide Photographic Material >> A corona discharge treatment was applied to both sides of a biaxially stretched and heat-set polyethylene phthalate film (thickness: 175 μm), and both sides were disclosed in JP-A-59-18945. The undercoat latex described in Example 1 was applied. Next, an antistatic layer having the following composition was applied to both surfaces thereof to prepare a support.

Water-soluble conductive polymer (P-1) 0.6 g / m ² Hydrophobic polymer (P-2) 0.5 g / m ² Curing agent (H-1) 2 × 10 ⁻³ / dm ²

[0187]

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The coating solution for the red-sensitive silver halide emulsion layer and the coating solution for the protective layer were applied on one surface of the support obtained. The silver content of the silver halide emulsion layer was 2.5 g / m ² , and the gelatin content was 1. 5
g / m ² and the gelatin amount of the protective layer was sequentially 0.8 g / m ² to form a red-sensitive silver halide emulsion layer and a protective layer. The coating solution for the lower backing layer and the coating solution for the upper backing layer were simultaneously coated with a slide hopper so that the amount of gelatin in the lower layer of the backing layer was 1.5 g / m ² and the amount of gelatin in the upper layer of the backing layer was 0.9 g / m ^2. A lower layer of the backing layer and an upper layer of the backing layer were formed to prepare a silver halide photographic material sample.

<< Evaluation of Long-Term Stability >> A wedge image of a 14 × 17 inch silver halide photographic material sample was printed with a semiconductor laser beam having a wavelength of 670 nm, and TCX-201 was used.
Using an automatic developing machine (modified TCX-201) modified from (Konica's automatic developing machine), processing time dry to dr at a developing temperature of 36 ° C., a fixing temperature of 35 ° C., and a drying temperature of 55 ° C.
Development processing was performed for y45 seconds.

In the modified TCX-201, the water washing mechanism in the development-fixing water lilac is modified so as to obtain a water supply amount of 5 to 8 cc / min.

The processing amount of the silver halide photographic light-sensitive material sample was 3.0 m ² per day, and the sample was operated for 8 hours per day while replenishing at the replenishment amount shown in Table 1. This process was repeated continuously every day.

A long-term running is performed as described above,
Sensitometry was determined on days 1, 15, 30, and 60 as follows. -Sensitometry evaluation-Sensitivity (S) is calculated from the reciprocal of exposure energy giving a density of fog + 1.0, and gamma (G) is fog +
It was determined as a gradient in a concentration range of 0.25 to +2.0.

In each process, the following developer α was used as the developer in the developing tank at the start, and the following developer replenisher α was used as the replenisher.

The results of the obtained treatment Nos. 1 to 16 are shown in Table 1. The sensitivity was shown as a relative sensitivity with the sensitivity of processing No. 1 being 100.

<< Developer α >> In the dissolution tank of the modified TCX-201, the following hydroquinone-based developing tablet α-1 was diluted with water.
And a solid developer tablet α composed of an alkali developer tablet α-2 was diluted and dissolved.

The solution of the solid developer tablet α was finely adjusted with acetic acid or potassium hydroxide so that the pH became 10.55.

The following starter was added to the prepared developing solution to fill a developing tank (7.8 liter). The starter addition amount was 35 ml / l.

(Starter Formulation) Potassium bromide 5.5 g HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH 0.05 g Acetyl-D, L-penicillamine 0.10 g Sodium metabisulfite The pH of the start solution is 10. Dilute to 45 ml with water.

<Solid developer tablet α> 100 as developer
Liter amount—Preparation of hydroquinone-based developing tablet α-1— (Preparation of granulated product (A)) Hydroquinone 2800 g, phenidone (1-phenyl-5-pyrazolidone) 300
g, boric acid 1000 g, N-acetyl-D, L-penicillamine 10 g and glutaraldehyde sodium bisulfite 500 g are each ground in a commercially available bandam mill until the average particle size becomes 10 μm. 700 g of sodium sulfite and binder D-Sorbit 20 are added to these fine powders.
0 g was added and mixed in the mill for 30 minutes. The resulting mixture was loaded into a commercial stirred granulator, 30 ml of water was added,
Granulate for about 5 minutes at room temperature. The obtained granules are dried at 40 ° C. for 2 hours in a fluidized bed drier to remove moisture of the granules,
A granulated product (A) was prepared. (Preparation of Hydroquinone Active Drug Developing Tablet α-1) Sodium 1-octanesulfonate (200 g) was added to the granulated product (A), and the mixture was humidified at 25 ° C. and 40% RH or less for 10 minutes using a mixer. Mix evenly. The obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho at a filling amount per tablet of 10 g, and a hydroquinone-based developing tablet α-1 was obtained.
Was prepared.

—Preparation of Alkaline Developing Tablet α-2— (Preparation of Granulated Material (B)) Each of 5300 g of potassium carbonate, 50 g of potassium bicarbonate, and 200 g of potassium bromide was prepared by using a commercially available bandam mill to have an average particle size of 10 μm. Crush until it becomes 200 g of lithium hydroxide hydrate, 250 g of DTPA.5H (diethylenetriaminepentaacetic acid), 5 g of 1-phenyl-5-mercaptotetrazole, 4000 g of sodium sulfite, and 1000 g of binder mannitol were added to the obtained powder, and the mixture was added to a mill. Minutes. The resulting mixture was charged into a commercially available stirred granulator,
Add ml water and granulate for about 15 minutes at room temperature. The obtained granulated product was dried at 40 ° C. for 2 hours with a fluidized bed drier to remove the water content of the granulated product to prepare a granulated product (B).

(Preparation of Alkaline Developing Tablet α-2) The granulated product (B) was treated with Kikusui Seisakusho's Tough Press Collect 1527H.
Using a tableting machine modified from U, the filling amount per tablet is 10
g and compression tableting was performed to prepare an alkali-developed tablet α-2. —Preparation of Solid Developing Tablet α— 3.4 liters of the obtained hydroquinone-based developing tablet α-1 and alkali developing tablet α-2 were placed in a pillow bag containing aluminum for moisture protection in an environment of 40% RH. The developer was sealed and packaged in such an amount as to obtain a solid developer α.

<< Development Replenisher α >> In the preparation of the solid developer tablet α, the amount of phenidone as a development auxiliary agent used in the preparation of the granulated product (A) is determined by changing the amount of the developer α in the developing tank at the start. (Development auxiliary agent) / (Development agent) of development replenisher α to (Development auxiliary agent) / (Development agent) [molar ratio]
Solid development replenishment tablet α was prepared in the same manner as solid development tablet α except that the molar ratio was changed to the value shown in Table 1 as “(adjuvant / main drug) magnification (vs. start solution)”. .

The packaging bag for the solid development replenishing tablet α was opened by hand, set in the inlet of the built-in chemical mixer, dropped the solid developing tablet into the built-in chemical mixer, and simultaneously poured warm water (25 to 30 ° C.) and stirred. While dissolving, 4.8 liters were prepared in a dissolution time of 20 minutes, and this was used as a development replenisher α
Used as In addition, fine adjustment was performed with acetic acid or potassium hydroxide so that the pH of the development replenisher became 10.55.

The developing replenisher α was used in the replenishing amount shown in Table 1.

Further, the fixing solution used in the above development processing is as follows.

<< Fixing solution >> The following solid fixing tablet was modified TC
It was prepared by diluting and dissolving with X-201 built-in chemical mixer with dilution water. The tablet was completely dissolved, and no precipitate was observed.

[0207] 7.0 liters of the adjusted fixing solution was used for remodeling T
CX-201 was placed in a fixing tank and used as a start solution.

Also, the solid fixing tablet packaging bag was opened by hand, set in the slot, dropped the solid fixing tablet into the built-in chemical mixer, and simultaneously poured hot water (25-30 ° C.) and dissolved while stirring and dissolving. 4.8 liters were prepared in 20 minutes and used as a fixing replenisher. The replenishment rate of the fixing replenisher is 1 per m ^{2 of the} silver halide photographic material sample.
It is 50 ml.

<Solid fixing tablet> 100 liter amount of fixing solution -Preparation of granulated product (E)-Ammonium thiosulfate / sodium thiosulfate (90/1)
15000 g in a commercially available banda mill until the average particle size becomes 10 μm. To this fine powder, 500 g of sodium sulfite, 750 g of sodium pyrosulfate and 1300 g of a binder (Pine Flow) are added, and the obtained mixture is charged into a commercially available stirring granulator, and 50 ml of water is added to perform granulation. The obtained granulated product was dried at 40 ° C. with a fluidized bed drier to substantially completely remove the water content of the granulated product, thereby preparing a granulated product (E).

-Preparation of Granulated Material (F)-400 g of boric acid, 1200 g of aluminum sulfate octahydrate,
1200 g of succinic acid and 300 g of tartaric acid are pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. 250 g of D-mannitol, 120 g of D-sorbit,
160 g of PEG # 4000 is added, and the resulting mixture is charged to a commercially available stirring granulator, and 30 ml of water is added to perform granulation. The obtained granules were dried at 40 ° C. with a fluidized bed drier to almost completely remove the moisture of the granules to prepare granules (F).

-Preparation of Solid Fixing Tablet- To the granulated product (E), 3000 g of β-alanine and 4330 g of sodium acetate were added, and sodium 1-octanesulfonate was further added to 1.5% of the total weight to obtain 25%. ° C
In a room humidified to 40% RH or less, 1
Mix uniformly for 0 minutes. The obtained mixture was subjected to compression tableting using a tableting machine modified from Kikusui Seisakusho's Tough Press Collect 1527H with a filling amount per tablet of 10.2 g to produce a cylindrical fixing tablet E having a diameter of 30 mm. did.

Further, 750 g of sodium metabisulfite was added to the granulated product (F), and sodium 1-octanesulfonate was further added to be 1.0% of the total weight.
In a room humidified to 40% RH or less, 1
Mix uniformly for 0 minutes. The obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527H manufactured by Kikusui Seisakusho at a filling amount per tablet of 11.2 g to produce a cylindrical fixing tablet F having a diameter of 30 mm. did.

The obtained fixing tablets E and F were sealed in a pillow bag containing aluminum for moisture-proofing in an amount of 3.4 liters of fixing solution to obtain a solid fixing agent. .

[0214]

[Table 1] As can be seen from Table 1, the method of the present invention has excellent long-term development processing stability in low replenishment processing.

Example 2 The procedure of Example 1 was repeated, except that the developing solution α in the developing tank at the start was changed to the following developing solution β, and the developing replenishing solution α was changed to the following developing replenishing solution β. Each development process was performed.

Table 2 shows the results of the obtained treatment Nos. 101 to 116. The sensitivity is shown as a relative sensitivity with the sensitivity of processing No. 1 of Example 1 being 100.

<< Developer β >> In the dissolution tank of the modified TCX-201, the following erythorbic acid-based developing tablet β-1 was diluted with water.
And a solid developing tablet β composed of an alkali developing tablet β-2 was prepared by dilution.

In the solution of the solid developing tablet β, fine adjustment was made with acetic acid or potassium hydroxide so that the pH became 10.35.

[0219] The following starter was added to the prepared developing solution to fill a developing tank (7.8 liter). The starter addition amount was 35 ml / l.

(Starter Formulation) Potassium bromide 5.5 g HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH 0.05 g Acetyl-D, L-penicillamine 0.10 g Sodium metabisulfite The pH of the start solution is 10. Dilute to 0 with water.

<Solid developer tablet β> 100 as developer
Liter amount-Preparation of erythorbic acid-based developing tablet β-1-2800 g of hydroquinone and 3500 g of erythorbic acid
Was prepared in the same manner as the hydroquinone-based developed tablet α-1, except that the tablet was replaced with the hydroquinone-based developed tablet α-1.

—Preparation of Alkali Developing Tablet β-2— An alkali developing tablet β-2 was prepared in the same manner as the alkali developing tablet α-2.

—Preparation of Solid Developing Tablet β— The obtained erythorbic acid-based developing tablet β-1 and alkali developing tablet β-2 are placed in a pillow bag containing aluminum for moisture-proofing in an environment of 40% RH. A quantity of 3.4 liters of the developing solution was sealed and packaged to obtain a solid developer β.

<< Development Replenisher β >> In the preparation of the erythorbic acid-based drug developing tablet β-1, the amount of phenidone as a development auxiliary agent used in the preparation of the granulated product (A) is determined by the amount of the developing agent in the developing tank at the start. Table 2 shows that (development auxiliary agent) / (developer agent) [molar ratio] of development replenisher β relative to (development auxiliary agent) / (developer agent) [molar ratio] in Table 2 shows “(auxiliary agent /
A solid development replenishment tablet β-1 was prepared in the same manner as the solid development tablet β-1, except that the ratio was changed to the value shown as “main agent) magnification (vs. start solution)”.

Further, an alkali developing tablet β-2 was prepared in the same manner as the alkali developing tablet α-2.

The resulting erythorbic acid-based developing tablet β-
1 and an alkali developing tablet β-2 are sealed and packaged in a pillow bag containing aluminum for moisture proofing in an environment of 40% RH in an amount of 3.4 liters of a developing solution to obtain a solid developer β. And

The packaging bag for the solid development replenishment tablet β was opened by hand, set in the inlet of the built-in chemical mixer, dropped the solid development tablet into the built-in chemical mixer, and simultaneously poured warm water (25 to 30 ° C.) and stirred. While dissolving, 4.8 liters were prepared in a dissolution time of 20 minutes, and this was used as a development replenisher α
Used as In addition, fine adjustment was performed with acetic acid or potassium hydroxide so that the pH of the developing replenisher became 10.35.

The developing replenisher β was used in the replenishing amount shown in Table 2.

[0229]

[Table 2]

As can be seen from Table 2, the method of the present invention shows excellent long-term development processing stability in low replenishment processing.

Example 3 Example 1 was repeated except that the developing solution α in the developing tank at the start was replaced by the following developing solution γ, and the developing replenishing solution α was replaced by the following developing replenishing solution γ. Each development process was performed.

Table 3 shows the results of the obtained treatment Nos. 201 to 216. The sensitivity is shown as a relative sensitivity with the sensitivity of processing No. 1 of Example 1 being 100.

<< Developer γ >> A starter is added to a developer prepared by a built-in chemical mixer modified so that it can be prepared in a modified TCX-201 three-part configuration from a concentrated developer kit having the following three-part configuration. Liquid (starting pH
9.90).

Composition of Concentrated Liquid Developing Kit (1 liter of developing solution) (Part A) Erythorbic acid 33 g Maison S (4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone) 3.3 g Potassium sulfite (50% aqueous solution) 70 g potassium bicarbonate 3 g potassium carbonate 80 g compound (AF-1) 0.4 g compound (AF-2) 0.10 g diethylene glycol 70 g 50% aqueous potassium hydroxide solution pH adjustment Finished to 550 ml with pure water, The pH was adjusted to 10.80.

(B part) Acetic acid (90%) 22 g Triethylene glycol 10 g N-acetyl-D, L-penicillamine 0.2 g Phenidone 2.0 g Dimezone S 4 g 5-Nitroindazole 0.02 g

(Part C) 5.0 g of 50% glutaraldehyde solution

<< Development Replenisher γ >> A replenishment solution γ is prepared from the concentrated developer kit having the above three-part composition by using a built-in chemical mixer modified so that the solution can be prepared in the three-part composition of modified TCX-201. (PH 10.10).

The amount of the maison S as a development auxiliary agent used in the preparation of the developer γ is determined by the following: (Development auxiliary agent) / (developer) [molar ratio] of the developer γ in the developing tank at the start.
Development replenisher γ to (development auxiliary agent) / (development agent) [molar ratio] with respect to, except that the value was changed to the value shown in Table 3 as “(auxiliary agent / agent) magnification (vs. start solution)”. The development replenisher γ was prepared in the same manner as the solution γ.

The developing replenisher γ was used in the amount shown in Table 3.

[0240]

[Table 3]

As can be seen from Table 3, the method of the present invention shows excellent long-term development processing stability in low replenishment processing.

Example 4 In Example 1, the developing solution α to which the starter was added in the developing tank at the start was replaced with the developing solution α shown in Tables 4 to 7.
β and γ were replaced with the developing solutions obtained by adding the starters described in Examples 1, 2 and 3, and the developing replenishing solution α was replaced with the corresponding developing replenishing solutions α, β and γ. Every 7 days (7 days, 14 days, 21 days, 28 days ...), the following developing agent tablets shown in Tables 4 to 7;
Table 4 shows the development auxiliary agent tablets and the thioether compound-containing tablets.
Each development process was carried out in the same manner except that the number of additions shown in Table 7 was added.

Tables 4 to 7 show the results of the obtained treatment Nos. 301 to 364. In addition, the sensitivity is the processing No. 1 of Example 1.
Is shown as a relative sensitivity with the sensitivity of 100 as 100. << Developing agent tablet >> Developing agent 1000 described in Tables 4 to 7
g, 100 g of sodium metabisulfite and 100 g of binder sorbitol were mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 15 minutes using a commercially available stirring granulator. The granulated product was dried at 40 ° C. for 2 hours using a fluidized bed drier to remove almost completely the water content of the granulated product.

In a room conditioned at 25 ° C. and 40% RH or less, the obtained granules were treated with sodium 1-octanesulfonate 2
After adding 0 g and mixing uniformly using a mixer for 10 minutes, the obtained mixture was adjusted to a filling amount per tablet of 5 g using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Then, compression tableting was performed to prepare a developing agent tablet. The developing agent tablet contains 4.1 g of the developing agent per tablet.

The obtained developing agent tablet was sealed and packaged in a pillow bag containing aluminum for moisture prevention.

<< Developing Auxiliary Agent Tablet >> 1000 g of developing auxiliary agent and sodium metabisulfite 10 shown in Tables 4 to 7
0 g and the binder D-Sorbit 80 g were mixed in a mill for 30 minutes, and the mixture was stirred at room temperature for 5 minutes using a commercially available stirring granulator.
After granulating by adding ml of water, the granulated product was dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the water content of the granulated product.

In a room conditioned at 25 ° C. and 40% RH or less, 15 g of sodium 1-octanesulfonate was added to the obtained granules, and the mixture was uniformly mixed for 10 minutes using a mixer. Using a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., the tablet was compressed and compressed at a filling amount of 5 g per tablet to give a diameter of 15 mm.
mm, a cylindrical development auxiliary agent tablet was prepared. The development auxiliary agent tablet contains 4.15 g of the development auxiliary agent per tablet.

The obtained tablets of the auxiliary developing agent were sealed and packaged in a pillow bag containing aluminum for moisture prevention.

<< Thioether Compound-Containing Tablet >> 1000 g of the thioether compound (I-8), 10 g of sodium metabisulfite, and 60 g of the binder D-sorbite were mixed in a mill for 30 minutes, and the mixture was stirred at room temperature using a commercial stirring granulator. After granulating the mixture by adding 30 ml of water for 5 minutes, the granulated product was dried at 40 ° C. for 2 hours with a fluidized bed drier to almost completely remove the water content of the granulated product.

In a room conditioned at 25 ° C. and 40% RH or less, 15 g of sodium 1-octanesulfonate was added to the obtained granules, and the mixture was uniformly mixed for 10 minutes using a mixer. Using a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., the tablet was compressed and compressed at a filling amount of 5 g per tablet to give a diameter of 15 mm.
mm-shaped thioether compound-containing tablets having a cylindrical shape were prepared. The thioether compound-containing tablets are listed in Tables 4 to 4 per tablet.
It contains 4.6 g of the thioether compound described in Table 7.

The obtained thioether compound-containing tablet was
It was sealed and packed in a pillow bag containing aluminum for moisture prevention.

[0252]

[Table 4]

[0253]

[Table 5]

[0254]

[Table 6]

[0255]

[Table 7] As can be seen from Tables 4 to 7, the method of the present invention has excellent long-term development processing stability in low replenishment processing.

[0256]

According to the method for processing a silver halide photographic light-sensitive material of the present invention, the silver halide photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains having a spectral maximum at 600 nm or more can be obtained. In the replenishment processing, excellent long-term development processing stability can be obtained.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer containing at least one silver halide grain having a spectral maximum at 600 nm or more on a support is developed by adding a replenisher. In the method, as the development replenisher, a development replenisher in which the molar ratio of the development auxiliary to the developing agent in the development replenisher is 1.1 times or more the molar ratio of the development auxiliary to the developer in the development start solution, And the replenishment rate is 50 ml / m ^{2 to} 200 ml /
method for processing a silver halide photographic light-sensitive material characterized in that the m ^2. 2. A silver halide photographic material having a silver halide emulsion layer containing at least one silver halide grain having a spectral maximum at 600 nm or more on a support is subjected to development processing by adding a development replenisher. A method for processing a silver halide photographic material, wherein a solid processing agent containing a developing agent is directly charged into a development processing tank during the development processing. 3. A silver halide photographic light-sensitive material having a silver halide emulsion layer containing at least one silver halide grain having a spectral maximum at 600 nm or more on a support is developed by adding a replenisher. A method for processing a silver halide photographic light-sensitive material, wherein a solid processing agent containing a development auxiliary agent is directly charged into a development processing tank during the development processing. 4. A silver halide photographic material having a silver halide emulsion layer containing at least one silver halide grain having a spectral maximum at 600 nm or more on a support is developed by adding a replenisher. A method for processing a silver halide photographic material, wherein a solid processing agent containing a thioether compound represented by the following general formula (1) is directly charged into a development processing tank during the development processing. General formula (1) A- (R ¹ -S) n-R ² -SR ³ -B [wherein R ¹ , R ² and R ³ represent an alkylene group or an alkylene group linked by an ether bond. . R ¹ ,
R ² and R ³ may form a ring with R ¹ and R ³ or R ² and R ³ . А and B may be the same or different and each represents a hydrogen atom, an alkyl group, an amino group, an ammonium group, a hydroxy group, a carboxy group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group. A and B may form a ring with A and B. n represents an integer of 0 to 10. ] 5. The replenishing amount of the developing replenisher is from 50 ml / m ² to
5. The pressure is set to 200 ml / m < ² >.
The processing method according to any one of the above. 6. The processing method according to claim 1, wherein the developing agent of the developer is a reductone.