JP2001174956A - Method for developing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for developing a black-and-white silver halide photographic sensitive material in which photographic performance is hardly varied even under slight replenishment, little unevenness is caused even in exposure with an image setter and a developing solution is hardly contaminated. SOLUTION: A photosensitive material in which the same or different silver halide emulsion layers provided on the substrate contain at least two kinds of silver halide emulsion having different sensitivities and at least one non- photosensitive hydrophilic colloidal layer contains non-photosensitive silver halide grains is continuously processed with a developing solution of pH 9.0-11.0 containing a compound of formula 1 (wherein at least one of R1-R4 is -SM, M is H or an alkali metal and the remainders are each H, halogen or other monovalent group but R1 and R3 are not OH) under replenishment with <=323 ml/m2 replenisher solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing method using a black-and-white silver halide photographic light-sensitive material which does not generate stains even in a solution having a pH of 11.0 or less. The present invention relates to a development processing method in which is reduced.

[0002]

2. Description of the Related Art Black-and-white silver halide photographic materials (hereinafter, referred to as "silver halide photographic materials").
It is simply called "black and white photosensitive material". ) Is after exposure, development,
An image can be obtained by performing fixing, washing or stabilizing treatment. Generally, a black-and-white photosensitive material has a developing section,
Development processing is performed by an automatic developing machine having a fixing section, a washing section or a stabilizing bath section and a drying section.

Conventionally, a photosensitive material is usually used to prevent the processing solution from being fatigued due to continuous processing or air oxidation.
m ² per 330ml or more developer replenisher and 450ml
The fact is that the processing has been performed while replenishing the above fixing replenisher. However, in recent years, disposal of the processing solution has become a problem with an increase in the processing amount, and the replenishment amount of the processing solution has been reduced due to the necessity of environmental pollution prevention. Further, there is also a problem that silver sulfite eluted from the photosensitive material in the developing tank is reduced to silver sludge, which contaminates the inside of the developing tank.

[0004] When this silver stain occurs, it deposits on the roller in the tank, causing a serious trouble such as being attached to the photosensitive material or being scratched. It is also known that when the amount of replenishment is reduced, the fluctuation of photographic properties increases.

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 improved. Further, Japanese Patent Application Laid-Open No. 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 spot failure is improved.

The claims of Japanese Patent Application Laid-Open No. 4-331951 contain a hydrazine derivative and have been subjected to color sensitization at a higher concentration per surface area of silver halide grains as compared with other silver halide grains. High contrast photosensitive materials characterized by silver halide grains are described. Further, the claims of British Patent Application Publication No. 9407599 include silver halide grains spectrally sensitized with a non-desorbable sensitizing dye and silver halide grains not spectrally sensitized,
High contrast photosensitive materials containing hydrazine derivatives are described. In both cases, due to the presence of the hydrazine derivative, the imagewise exposure and development contribute to the silver image in which the photosensitive particles and the non-photosensitive particles that are not spectrally sensitized are formed by the imagewise exposure and development, and the sensitivity and the sensitivity are high. While maintaining the concentration,
This has the effect of saving the sensitizing dye and improving the residual color.

These photographic materials are excellent in processing stability, contrast, sensitivity, and residual color, but have the drawback that when an image setter outputs 60% to 90% of a flat screen, exposure unevenness occurs.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a stable developer having a pH of 11.0 or less and a small variation in photographic performance even if the replenishment amount of the developer is small. It is another object of the present invention to provide a method for processing a silver halide black-and-white photographic light-sensitive material, which is less likely to cause unevenness, generates less stains on a developing solution or a light-sensitive material, and always provides stable performance.

[0009]

An object of the present invention is to provide at least two silver halide emulsions having the same or different silver halide emulsion layers having different sensitivities provided on a support. In a method for developing a silver halide photographic material in which at least one hydrophilic colloid layer other than the silver halide emulsion layer contains at least one kind of non-photosensitive silver halide grain, the following general formula (I) The amount of replenishment of a developer containing a compound represented by the formula (1) and having a pH of 9.0 to 11.0 (meaning “from 9.0 to 11.0, the same applies hereinafter”). 323 ml / m
Achieved by a method for developing a black-and-white silver halide photographic light-sensitive material, characterized in that continuous development processing is carried out as ² or less. General formula (I)

[0010]

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In the general formula (I), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. However, R ₁ and R ₃ do not represent a hydroxy group. R _{1 to} R ₄ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Here, the compound of the formula (I) will be described in detail. R _{1 to} R ₄ are a hydrogen atom, a halogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom,
Represents an arbitrary substituent bonded to the ring by a phosphorus atom. Where R ₁
And R ₃ do not represent a hydroxy group. R _{1 to} R ₄
May be the same or different, but at least one of R _{1 to} R ₄ represents a —SM group (M is an alkali metal atom,
Hydrogen atom, ammonium group). Specific examples of the optional substituents of R _{1 to} R ₄ include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), an alkyl group (including an aralkyl group, a cycloalkyl group, and an active methine group). An alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a quaternary heterocyclic group containing a nitrogen atom (for example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or Its salts, sulfonylcarbamoyl groups,
Acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group,
Cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group Carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido Group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group,
Hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl or heterocyclic) thio group, Including (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid amide or phosphate ester structure Groups, and the like. However, R ₁ and R ₃ do not represent a hydroxy group.

These substituents may be further substituted with these substituents.

More preferably, the substituent of R _{1 to} R ₄ is
A substituent having 0 to 15 carbon atoms, a chloro atom, an alkyl group,
Aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, carboxy group or salt thereof, cyano group, alkoxy group, aryloxy group, acyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, Hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or A heterocycle) thio group, a sulfo group or a salt thereof, and a sulfamoyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an alkoxy group, an aryloxy group, Acyloxy group,
Amino group, (alkyl, aryl or heterocycle) amino group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino Group, mercapto group, (alkyl, aryl or heterocycle) thio group, sulfo group or a salt thereof, most preferably amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group , An alkylthio group, an arylthio group, a mercapto group, a carboxy group or a salt thereof, a sulfo group or a salt thereof. In the general formula (I), at least one of R _{1 to} R ₄ is a —SM group, and more preferably, at least two of R _{1 to} R ₄ are a —SM group. If at least two of R ₁ to R ₄ is a -SM group, preferably the R ₄ and R _1, or R ₄ and R ₃ -SM group.

In the general formula (I), M represents an alkali metal atom, a hydrogen atom, or an ammonium group. Here, the alkali metal atom is specifically Na, K, Li, Mg, Ca or the like, and these exist as counter cations of -S-.
M is preferably a hydrogen atom, an ammonium group, Na
⁺ Or K ⁺ , and particularly preferably a hydrogen atom.

In the present invention, among the compounds represented by the general formula (I), the compounds represented by the following general formulas (1) to (3) are particularly preferred.

[0017]

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In the general formula (1), R ₁₀ represents a mercapto group, a hydrogen atom, or an arbitrary substituent, and X represents a water-soluble group or a substituent substituted with a water-soluble group. In the general formula (2), Y ₁ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₂₀ represents a hydrogen atom or an arbitrary substituent. In Formula (3), Y ₂ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₃₀ represents a hydrogen atom or an arbitrary substituent. However, R ₁₀ and Y ₁ do not represent a hydroxy group.

Next, the compounds represented by formulas (1) to (3) will be described in detail. In the general formula (1), R ₁₀ represents a mercapto group, a hydrogen atom or an arbitrary substituent. However, R ₁₀ does not represent a hydroxy group. Here, the optional substituents are the same as those described for R _{1 to} R _{4 in} formula (I). R ₁₀ is preferably a mercapto group, a hydrogen atom, or a group having 0 to 0 carbon atoms.
It is a group selected from the following 15 substituents. That is,
Amino group, alkyl group, aryl group, alkoxy group, aryloxy group, acylamino group, sulfonamide group,
Alkylthio group, arylthio group, alkylamino group,
Arylamino groups and the like. In the general formula (1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group is a sulfonic acid or a carboxylic acid and a salt thereof, a salt such as an ammonio group, or a group containing a dissociable group which can be partially or completely dissociated by an alkaline developer. Has a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonium group,
It represents a sulfonamide group, an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, or a substituent containing these groups. In the present invention, the active methine group refers to a methyl group substituted with two electron-withdrawing groups, and specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy And groups such as carbonylmethyl. X in general formula (1)
The substituent represented by is a water-soluble group described above, or a substituent substituted with the above-described water-soluble group, and the substituent is a substituent having 0 to 15 carbon atoms, such as an alkyl group or an aryl group. Group, heterocyclic group, alkoxy group, aryloxy group,
Heterocyclic oxy, acyloxy, (alkyl, aryl or heterocyclic) amino, acylamino, sulfonamide, ureido, thioureido, imide, sulfamoylamino, (alkyl, aryl or heterocycle) thio Group, (alkyl, aryl) sulfonyl group, sulfamoyl group, amino group, etc., preferably an alkyl group having 1 to 10 carbon atoms (particularly a methyl group substituted with an amino group), an aryl group, an aryloxy group, an amino group Group, (alkyl, aryl, or heterocycle) amino group, (alkyl, aryl, or heterocycle)
It is a group such as a thio group.

Among the compounds represented by the general formula (1), more preferred are the compounds represented by the following general formula (1-a).

[0021]

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Where R₁₁Is R of the general formula (1)_TenSynonymous with
The preferred range is also the same. R ₁₂, R₁₃Are each
May be the same or different, and include a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group. Where R₁₂You
And R₁₃At least one is at least one water-soluble
Having a group. Here, the water-soluble group refers to a sulfo group (or a sulfo group).
), Carboxy group (or its salt), hydroxy
Group, mercapto group, amino group, ammonium group, sulfone
Amide group, acylsulfamoyl group, sulfonylsulf
Amoyl group, active methine group, or a group containing these groups
And preferably represents a sulfo group (or a salt thereof),
Ruboxy group (or its salt), hydroxy group, amino group
And the like. R₁₂And R₁₃Is preferably
A alkyl group or an aryl group;₁₂And R₁₃But
When it is a alkyl group, the alkyl group has 1 to 4 carbon atoms.
Is preferably a substituted or unsubstituted alkyl group.
As the substituent, a water-soluble group, particularly a sulfo group (or
Salt), carboxy group (or its salt), hydroxy group,
Or an amino group is preferred. R₁₂And R₁₃Is aryl
When it is a group, the aryl group has 6 to 10 carbon atoms.
A substituted or unsubstituted phenyl group is preferred.
As the group, a water-soluble group, particularly a sulfo group (or a salt thereof),
A carboxy group (or a salt thereof), a hydroxy group, or
Amino groups are preferred. R₁₂And R₁₃Is an alkyl group or
When represents an aryl group, these are linked to each other to form a ring
A structure may be formed. It is saturated by the ring structure
A hetero ring may be formed.

In the general formula (2), Y ₁ represents a water-soluble group or a substituent substituted with a water-soluble group;
X is synonymous. However, Y ₁ does not represent a hydroxy group. In formula (2), the water-soluble group represented by Y ₁ or a substituent substituted with a water-soluble group is more preferably an active methine group or the following group substituted with a water-soluble group, namely, an amino group, An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group, and an aryl group. More preferably, Y ₁ is an active methine group or an amino group substituted with a water-soluble group (alkyl, aryl, or heterocycle), wherein the water-soluble group is a hydroxy group, a carboxy group or a salt thereof, or a sulfo group. Groups or salts thereof are particularly preferred. Particularly preferred as Y ₁ is an (alkyl, aryl, or heterocycle) amino group substituted with a hydroxy group, a carboxy group (or a salt thereof), or a sulfo group (or a salt thereof), and —N (R ₀₁ ) (R ₀₂ ). Here, R ₀₁ and R ₀₂ are R ₁₂ and R _{13 in the} general formula (1-a), respectively.
And the preferred range is also the same.

In the general formula (2), R ₂₀ represents a hydrogen atom or an optional substituent, wherein the optional substituent is the same as that described for R _{1 to} R _{4 in} the general formula (I). Is raised. R ₂₀ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms.
That is, examples include a hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a hydroxylamino group. Most preferably, R ₂₀ is a hydrogen atom.

In the general formula (3), Y ₂ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₃₀ represents a hydrogen atom or any substituent. Y in general formula (3)
₂ and R ₃₀ are groups having the same meaning as Y _{1 in} the general formula (2) and R _{20 in the} general formula (2), respectively, and the preferred ranges are also the same.

Hereinafter, specific examples of the compound represented by formula (I) of the present invention will be shown, but it goes without saying that the present invention is not limited to these.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The addition amount of the compound of the formula (I) is 0.01 to 10 mmol, preferably 0.1 to 5 mmol, per liter of the working solution. When it is added to a silver halide photographic material, it is preferably added to a non-photosensitive layer such as a back layer or the uppermost protective layer. In this case, the range is preferably from 1 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol per 1 m ^{2 of} the photosensitive material, and particularly preferably from 1 × 10 ⁻⁵ mol to 1 × 10 ⁻³ mol. Further, the compound of the general formula (I)
They may be used alone or in combination.

The silver halide emulsion and the non-light-sensitive silver halide grains used in the silver halide photographic light-sensitive material of the present invention are not particularly limited as silver halide, and silver chloride, silver chlorobromide,
Silver bromide, silver iodochlorobromide and silver iodobromide can be used, but silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride are preferred. The shape of silver halide grains is cubic,
Any of a tetrahedron, an octahedron, an irregular shape, and a plate shape may be used, but a cube is preferable. The average grain size of silver halide is 0.1 μm
To 0.7 μm, more preferably 0.1 to
It is preferable that the particle size distribution is 0.5 μm and the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10% or less, and the particle size distribution is narrow. In the silver halide grains, the inside and the surface layer may have a uniform phase or may be different. Further, a localized layer having a different halogen composition may be provided inside or on the surface of the grain.
The photographic emulsion used in the present invention is Chim's P. Glafkides.
ie etPhysique Photographique (Paul Montel, 1
967), Photographic Emulsion Ch by GF Dufin
emistry (The Forcal Press, 1966), VLZe
Making and Coating Photographic Emu by likman et al
lsion (The ForcalPress, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt with a soluble halide salt may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. Is also good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, 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 preferred are tetra-substituted thiourea compounds.
No. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent to be added varies depending on the kind of the compound used, the intended grain size, and the halogen composition, but is preferably from 10 ^-5 to 10 ^-2 mol per mol of silver halide.

In the controlled double jet method and the grain formation 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, and is used in the present invention. It is a useful tool for making silver halide emulsions. Also, in order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above item to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodispersed emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
It is 1 μm to 0.4 μm.

The non-photosensitive silver halide grains of the present invention have a blue range sensitivity of 1/10 or less of the photosensitive silver halide grains used in the photographic material of the present invention, and must not be spectrally sensitized. Is preferred. The amount of the non-photosensitive silver halide grains used in the present invention is 0.01 g / m ² to 1 g.
/ M ² , more preferably 0.03 g / m ² to 0.5 g / m ² . The hydrophilic colloid layer containing the non-light-sensitive silver halide grains of the present invention may be provided as an antihalation layer (AH) closer to the support than the light-sensitive silver halide emulsion layer, or may be farther away. One or more protective layers may be provided at positions.

The silver halide emulsion used in the present invention is:
It may contain a metal belonging to Group VIII. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, or the like. In addition, K ₄ (Fe (C
Doping of a metal hexacyanoide complex such as N) ₆ ], K ₄ [Ru (CN) ₆ ], or K ₃ [Cr (CN) ₆ ] is advantageously performed. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, rhodium (III) halide compounds or rhodium complex salts having halogens, amines, oxalato, aquo, etc. as ligands, for example, hexachlororhodium (III) complex salt, pentachloroacolodium complex salt, tetrachlorodiacolate Rhodium complex,
Hexabromorhodium (III) complex salt, hexaaminerhodium (III) complex salt, trizalatrodium (III) complex salt and the like can be mentioned. These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the rhodium compound is generally used, that is, an aqueous solution of hydrogen halide (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KC
1, NaCl, KBr, NaBr, etc.). Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain doped with rhodium in the preparation of silver halide.

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and JP-A-Hei.
Nos. -285941 and 2-20852 and 2-208
No. 55, etc. in the form of a water-soluble complex salt. Particularly preferred are hexacoordinate complexes represented by the following formula. [ML _{6] -n} wherein M represents Ru, Re or O _s,, n is 0,
Represents 1, 2, 3 or 4. In this case, the counter ion is not important and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^-3 [ReBr ₆ ] ^-3 [ReCl ₅ (NO)] ^-2 [Re (NS) Br ₅ ] ^-2 [Re (NO) (CN) ₅ ] ^-2 [Re (O ) ₂ (CN) ₄ ] ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)] ^-2 [Ru (CO) ₃ Cl ₃ ) ^-2 [Ru (CO) Cl ₅ ] ^-2 [Ru (CO) Br ₅ ] ^-2 [O _s Cl ₆ ] ^-3 [O _s Cl ₅ (NO)] ^-2 [O _s (NO ) (CN) _5] ^-2 [O _s (NS) Br _5] ^-2 [O _s (CN) _6] ^-4 _{[O s (O) 2 (CN} ) 5 ] ^-4

The addition amount of these compounds is 1
1 × 10 per mole^-9Mol ~ 1 x 10 ^-FiveMolar range preferred
And particularly preferably 1 × 10^-8Mol ~ 1 x 10^-6Mole
It is. As the iridium compound used in the present invention
Is hexachloroiridium, hexabromoiridium
System, hexaammineiridium, pentachloronitrosi
Louisiridium and the like. Lute used in the present invention
Hexachlororuthenium, pen
Tachloronitrosyl ruthenium. In the present invention
As the iron compound used, hexacyanoferrate (II) acid
Potassium and ferrous thiocyanate.

The silver halide emulsion of the present invention is preferably subjected to chemical sensitization. As the method of chemical sensitization, 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 these are used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by
Add a yellow sensitizer and keep the emulsion at a high temperature of 40 ° C or more.
It is performed by stirring for a while. Public sulfur sensitizer
Known compounds can be used, for example, in gelatin
In addition to the sulfur compounds contained in, various sulfur compounds,
For example, thiosulfates, thioureas, thiazoles, rhodani
And the like can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. Addition of sulfur sensitizer
The amount depends on the pH, temperature and the size of silver halide grains during chemical ripening.
Changes under various conditions such as
10 per mole ^-7-10^-2Mole, more preferably
10^-Five-10^-3Is a mole.

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. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
The compounds described in JP-A-4-109240 and JP-A-4-324855 can be used. In particular, JP-A-4-3
It is preferable to use compounds represented by formulas (VIII) and (IX) in 24855.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in US Pat.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibi
d 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 O, The Chemistry of Organic Selenium and Tellurium Company
rganic Selenium and Tellunium Compounds), Vol 1
(1986) and the compounds described in Vol. 2 (1987) can be used. Particularly, compounds represented by formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is 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 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added by the method described in European Patent Publication (EP) 293917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind, or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, different habits, different chemical sensitization conditions, and different sensitivities) may be used in combination. Above all, in order to obtain high contrast, Japanese Patent Application Laid-Open
As described in JP-A-324426, it is preferable to coat an emulsion having a higher sensitivity as it is closer to the support.

The hydrazine derivative used in the present invention will be described. In the present invention, the compound of the general formula (I) described in JP-A-7-287335 is used. Specifically, compounds represented by I-1 to I-53 described in the same specification are used.

The following hydrazine derivatives are also preferably used. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, the compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, from pages 8 to 1 of the publication
Compounds 1 to 38 on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4-1 to 4-10 described on page 26, compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formulas (1) and (2) described in JP-A-6-289520, specifically from page 5 to
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H described on pages 8 to 15 of the same publication
-1 to H-44. JP-A-9-22082, a compound characterized by having an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, particularly a compound represented by the general formula (A): Formula (B), Formula (C), Formula (D), Formula (E),
Compounds represented by formula (F), specifically, compounds N-1 to N-30 described in the same publication. JP-A-9-22082
And the compounds represented by the general formula (1), specifically, compounds D-1 to D-55 described in the same publication.

The hydrazine-based nucleating agent that can be used in the present invention includes a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone),
It can be used by dissolving in dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also,
By an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and the emulsified dispersion is mechanically dispersed. It can be manufactured and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine nucleating agent of the present invention is applied to a support.
And the silver halide emulsion layer on the side of the silver halide emulsion layer
Or any other hydrophilic colloid layer
Are hydrophilic or adjacent to the silver halide emulsion layer.
It is preferable to add it to the hydrophilic colloid layer. Nucleation of the present invention
The amount of the additive was 1 × 10 5 per mole of silver halide.^-6~ 1 ×
10^-2Mole is preferred and 1 × 10^-Five~ 5 × 10^-3Mole
More preferably 2 × 10 ^-Five~ 5 × 10^-3Mole is most preferred
New

The nucleation accelerator used in the present invention includes
Examples include an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds (A-1 to A-73) described on pages 49 to 58. JP-A-7-84
No. 331, (Chem. 21), (Chem. 22) and (Chem. 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. The general formulas (1), (2), (3), (4) described in JP-A-8-272023,
Compounds represented by the general formulas (5), (6) and (7), specifically, 1-1 to 1 described in the same specification.
-19, 2-1 to 2-22, 3-1 to 2-1
Compound of 3-36, compound of 4-1 to 4-5, 5-1 to
Compounds of 5-41, compounds of 6-1 to 6-58 and 7
-1 to 7-38. A nucleation accelerator described in JP-A-9-297377.

The nucleation accelerator of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves and used by a method known as a solid dispersion method.

The nucleation accelerator of the present invention may be added to any layer of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × 10 per mol of silver halide.
^-2 mol is preferable, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferable.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include those described or cited in, for example, RESEARCH DISCLOSURE Item 17643 IV-A (p.23, December 1978) and Item 1831X (p.437, August 1979). Has been described. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected.
For example, A) for an argon laser light source, (I) -1 to (I)-described in JP-A-60-162247.
No. 8, compound I-1 to I-28 described in JP-A-2-48653, compound I-1 to I-13 described in JP-A-4-330434, U.S. Pat.
No. 331, the compounds of Examples 1 to 14, the compounds of 1 to 7 described in German Patent 936,071, and B) a helium-neon laser light source. Compounds of I-1 to I-38, I-1 to I-38 described in JP-A-6-75322
-35 and compounds I-1 to I-34 described in JP-A-7-287338; C) For LED light sources, dyes 1 to 2 described in JP-B-55-39818.
0, I-1 to I described in JP-A-62-284343.
-37 and the compounds of I-1 to I-34 described in JP-A-7-287338; and D) For the semiconductor laser light source, the compounds described in JP-A-59-191032.
Compounds 1 to I-12, compounds of I-1 to I-22 described in JP-A-60-80841, JP-A-4-335
Compounds I-1 to I-29 described in JP-A-342-342 and I-1 to I-18 described in JP-A-59-192242.
E) Compounds (1) to (19) represented by the general formula [I] described in JP-A-55-45015 for a tungsten and xenon light source of a plate-making camera, and JP-A-9-160185. And the 4-A compounds described in JP-A-6-242547.
To 4-S, 5-A to 5-Q, 6-
Compounds from A to 6-T are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclos.
ure) 176, 17643 (issued December 1978) No. 2
Section J on page 3, IV, or JP 49-25500, 4
3-4933, JP-A-59-19032 and JP-A-59-19.
2242 and the like.

Two or more sensitizing dyes may be used in combination in the present invention. The sensitizing dyes may be added to the silver halide emulsion by dispersing them directly in the emulsion or by using water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025, etc., a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-51-723, and JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion.
As disclosed in Japanese Patent No. 74624, a method in which a dye is dissolved using a compound that causes a red shift, and the solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Patent Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the step of forming silver halide grains and / or before desalting, during and / or after desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. And 4 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The light-sensitive material prepared by using the present invention may contain a solid disperse dye as a filter dye or for various purposes such as prevention of irradiation. The dyes preferably used include the general formula (FA), the general formula (FA1) and the general formula (FA) described in JP-A-9-179243.
2), a dye represented by the general formula (FA3), specifically, compounds F1 to F34 described in the publication. Further, (II-2) to (II-24) described in JP-A-7-152112,
(III-5) to (III-1) described in JP-A-7-152112
8), (IV-2)-described in JP-A-7-152112
(IV-7) is also preferably used.

Other dyes that can be used in the present invention include solid fine particle dispersed dyes that are decolorized during processing, such as cyanine dyes, pyrylium dyes and aminium dyes described in JP-A-3-138640. Examples of the non-dye include cyanine dyes having a carboxyl group described in JP-A-9-96891 and JP-A-8-245.
No. 902, a lake type cyanine dye described in JP-A 8-333519, a cyanine dye described in JP-A-1-266536, and a cyanine dye described in JP-A-3-266519.
Solid fine particle dispersion of a holopolar cyanine dye described in 136038, a pyrilium dye described in JP-A-62-299959, a polymer-type cyanine dye described in JP-A-7-253039, and an oxonol dye described in JP-A-2-282244; Light scattering particles described in JP-A-63-131135, Yb ³⁺ compounds described in JP-A-9-5913, and ITO powders described in JP-A-7-113072 are exemplified. In addition, dyes represented by formulas (F1) and (F2) described in JP-A-9-179243, specifically, compounds F35 to F112 described in the same publication can also be used.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and benzylidene dyes are useful. Specific examples of dyes that can be used are described in British Patent Nos. 584,609 and 1,177,42.
No. 9, JP-A-48-85130 and JP-A-49-99620.
No. 49-114420, No. 52-20822,
Nos. 59-154439 and 59-208548, U.S. Pat. Nos. 2,274,782 and 2,533,472
Nos. 2,956,879 and 3,148,187
No. 3,177,078, 3,247,127
No. 3,540,887 and 3,575,704
No. 3,653,905 and 3,718,427.

In the silver halide emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic properties (for example, For various purposes, such as development acceleration, high contrast, and sensitization, various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, Nonionic surfactants such as polyethylene oxide adducts of silicone), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylate , Alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, Carboxyl groups such as alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, and the like. Surfactant containing an acidic group such as a group, a sulfo group, a phospho group, a sulfate group or a phosphate group; an amino acid, an aminoalkylsulfonic acid, an aminoalkyl sulfate or a phosphate, an alkyl betaine, an amine Amphoteric surfactants such as oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring Etc. It can be used a surfactant.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5; Specifically, compounds (III) -1 to 25 described in the publication.

A compound represented by the general formula (I) described in JP-A-1-11832 and having substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, fourth line.

The polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. A polymer latex having an active methylene group represented by the general formula (I) described in JP-A-9-179228, specifically, compounds I-1 to I-l described in the same specification.
I-16. Polymer latex having a core / shell structure described in JP-A-9-179228, specifically, compounds P-1 to P-55 described in the same specification. JP-A-7-1
An acidic polymer latex described on page 14, left line 1 to page 30, right line of JP-A-04413, specifically, compounds II-1) to II-9) described on page 15 of the same.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

Hardeners described in JP-A-2-103536, page 18, upper right line, 5th line to upper right line, 17th line.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right, line 6 to page 19, upper left, first line.

JP-A-2-18542, page 2, lower left 1
The conductive substance described in the third line to the upper right line on page 3 of the publication. Specifically, the metal oxides described on page 2, right lower second line to page 10 lower right line, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1) described in the publication,
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

JP-A-2-18542, page 3, lower right
The binder described in the second to 20th lines.

Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

The silver halide light-sensitive material of the present invention is developed with a developing solution containing a dihydroxybenzene-based developing agent or an ascorbic acid-based developing agent as a developing agent and an auxiliary developing agent having superadditivity with the developing agent. At the time of the development processing, a normal automatic development processor can be used. The developing solution filled in the developing tank at the start of development is called a developing start solution (mother solution), and the developing solution replenished to the developing tank during continuous development is called a developing replenisher. In the present invention, both the developing start solution and the developing replenisher contain a dihydroxybenzene-based developing agent or an ascorbic acid-based developing agent as a developing agent and an auxiliary developing agent showing superadditivity with the developing agent.

The dihydroxybenzene-based developing agent used in the present invention includes hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, hydroquinone monosulfonate, etc., with hydroquinone being particularly preferred. Auxiliary developing agents that exhibit superadditivity with dihydroxybenzene-based developing agents include 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-pyrazolidone or a combination of a dihydroxybenzene-based developing agent and a p-aminophenol is preferably used. The developing agents of 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. The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-
Hydroxyphenyl) glycine, etc., among which N
-Methyl-p-aminophenol is preferred. The dihydroxybenzene-based developing agent is usually 0.05 to 0.8 mol /
It is preferably used in an amount of liter, but in the present invention, it is particularly preferable to use it in an amount of 0.23 mol / liter or more. More preferably, 0.23-0.6 mol /
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 / l, more preferably 0.23 ~
0.5 mol / l, the latter being 0.06 mol / l or less, more preferably 0.03 mol / l to 0.1 mol / l.
It is preferably used in an amount of 003 mol / l.

In the present invention, both the development start solution and the development replenisher have the property that “the rise in pH when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.5 or less”. Is preferred. As a method for confirming that the developing solution or replenisher used has this property, the pH of the developing solution or replenisher to be tested is adjusted to 1
The solution was adjusted to 0.5, and then 0.1 mol of sodium hydroxide was added to 1 liter of the solution. The pH value of the solution at this time was measured. It is determined to have properties. In the present invention, it is particularly preferable to use a development start solution and a development replenisher whose rise in pH value in the above test is 0.4 or less.

As a method for imparting the above properties to the development starting solution and the development replenisher, it is preferable to use a buffer.
Examples of the buffer include carbonates, boric acid described in JP-A-62-186259, sugars (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5 -Sulfosalicylic acid), tertiary phosphates (e.g., sodium salt, potassium salt) and the like, and preferably carbonate and boric acid. The amount of buffer, especially carbonate used, is preferably
It is at least 0.25 mol / l, especially 0.25 to 1.5 mol / l.

In the present invention, the pH of the developing solution is from 9.0 to 11.0, preferably from 9.5 to 11.0.
The range is 0.7. The pH of the developer replenisher and the pH of the developer in the developing tank during continuous processing are also in 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 a silver halide photographic light-sensitive material, the replenisher amount of the developing solution is 323 ml or less, preferably 323 to 30 ml, particularly 2 ml.
25 to 50 ml. The development replenisher may have the same composition as the development initiating liquid, or may have a higher concentration of components consumed in development than the initiating liquid.

In the present invention, a developing solution used for developing a light-sensitive material (both a developing solution and a developing replenisher are collectively referred to as a developing solution; hereinafter the same) is used as a commonly used additive (for example, a preservative). , Chelating agents). Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. 0.2 sulfite
It is used in an amount of 0 mol / l or more, particularly 0.3 mol / l or more. However, if it is added in an excessively large amount, it causes silver contamination in the developer, so the upper limit is preferably 1.2 mol / l. Particularly preferably, it is 0.35 to 0.7 mol / liter. As a preservative of the dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with a sulfite. Here, the ascorbic acid derivative includes ascorbic acid, its stereoisomer erythorbic acid, and its alkali metal salts (sodium and potassium salts). It is preferable to use sodium erythorbate from the viewpoint of material cost. The amount of addition is 0.03-
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.

The additives used other than those described 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 and derivatives thereof; mercapto A compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be contained as an antifoggant or a black pepper inhibitor. 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-
Sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer.

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

Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67.
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
Hydroxyalkylidene-diphosphonic acid described in No. 227639 and the like;
Disclosure) Volume 181, Item 18170 (1979
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. No. 61125, 5
Compounds described in JP-A-5-29883 and JP-A-56-97347 can be exemplified.

Examples of the organic phosphonocarboxylic acid include JP-A-52-102726, JP-A-53-42730, and JP-A-54-42730.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65555
And the compounds described in Research Disclosure No. 55-65556, and Research Disclosure No. 18170 described above. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt.

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

Examples of the aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67.
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
Hydroxyalkylidene-diphosphonic acid described in No. 227639 and the like;
Disclosure) Volume 181, Item 18170 (1979
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. No. 61125, 5
Compounds described in JP-A-5-29883 and JP-A-56-97347 can be exemplified.

The organic phosphonocarboxylic acid is disclosed in
No. 52-102726, No. 53-42730, No. 54
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65555
No. 55-65556, and the aforementioned Research D
Compounds described in Scrougeer 18170 and the like are listed.
be able to. These chelating agents include alkali metal salts and
It may be used in the form of an ammonium salt. These chelates
The addition amount of the agent is preferably
Is 1 × 10^-Four~ 1 × 10^-1Mole, more preferably 1 ×
10^-3~ 1 × 10 ^-2Is a mole.

Further, as a silver stain preventive agent in a developer, 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, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color tone agent, a surfactant,
It may contain an antifoaming agent, a hardening agent and the like. The development processing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the development temperature is about 20 ° C. to about 50 ° C., preferably 25 ° C. to 45 ° C. Minutes, preferably 7 seconds to 1 minute 30 seconds.

It is preferable to concentrate the processing liquid and dilute it at the time of use for the purpose of transport cost of the processing liquid, packaging material cost, space saving, and the like. For concentration of the developer, it is effective to convert a salt component contained in the developer into potassium salt.

The fixing solution used in the fixing step includes sodium thiosulfate, ammonium thiosulfate, tartaric acid if necessary,
It is an aqueous solution containing a salt of citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tiron, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, or salts thereof. From the viewpoint of environmental protection in recent years, it is preferable that boric acid is not contained.
The fixing agent of the fixing solution used in the present invention is sodium thiosulfate, ammonium thiosulfate or the like, and ammonium thiosulfate is preferable from the viewpoint of fixing speed, but sodium thiosulfate may be used from the viewpoint of environmental protection in recent years. . The amount of these known fixing agents can be varied as appropriate, and is generally about 0.1 to about 2 mol / l. Particularly preferably, it is 0.2 to 1.5 mol / l.
The fixing solution may optionally contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), and a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing promoters. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
And the amphoteric surfactants described in JP-A-6740. In addition, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754, 58-122535, and 5
No. 8-122536, thiourea derivatives, alcohols having a triple bond in the molecule, US Pat.
No. 59, thioether compounds described in JP-A-4-2298.
No. 60 meso-ionic compound, and the like.
Compounds described in JP-A-2-44355 may be used.
Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, adipic acid, and inorganic acids such as boric acid, phosphate, and sulfite. Buffers can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffer is used for the purpose of preventing the pH of the fixing agent from increasing due to carry-in of the developing solution, and is used in an amount of 0.01 to 1.0 mol / l, more preferably about 0.02 to 0.6 mol / l. . The pH of the fixing solution is preferably from 4.0 to 6.5, and particularly preferably from 4.5 to 6.0. Further, compounds described in JP-A-64-4739 can be used as the dye elution accelerator.

The hardener in the fixing solution of the present invention includes a water-soluble aluminum salt and a chromium salt. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate and potassium alum. A preferable addition amount is 0.01 mol to 0.2 mol / l, and more preferably 0.03 to 0.08 mol / l. The fixing temperature is about 20 ° C. to about 50 ° C., preferably 25 ° C.
At ~ 45 ° C, the fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is not more than 600 ml / m ² , especially 500 ml / m ^{2 with} respect to the processing amount of the photosensitive material.
m ² or less, more preferably 300 ml / m ² or less.

The photosensitive material which has been developed and fixed is then washed or stabilized. In the washing or stabilizing treatment, the washing water amount is usually per 1 m ^{2 of the} silver halide photosensitive material,
It is carried out with 20 liters or less, and can be carried out with a replenishment amount of 3 liters or less (including 0, that is, washing with water). That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of the washing water, a multi-stage countercurrent method (for example, two-stage, three-stage, or the like) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in a normal direction, that is, a processing solution that is not contaminated with the fixing solution, so that processing is more efficient. Washing is performed. When the washing is performed with a small amount of water, see Japanese Unexamined Patent Publication No.
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 18350 and 62-287252. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in
As described in JP-A-235133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness which is likely to be generated when washing with a small amount of water and / or to prevent a processing agent component adhering to a squeeze roller from being transferred to a processed film. Good. Further, in order to prevent contamination by dyes eluted from the photosensitive material, JP-A-63-16
The dye adsorbent described in No. 3456 may be installed in a washing tank. In some cases, a stabilization treatment may be performed after the water washing treatment.
Nos. 132435, 1-125553, and JP-A-46-46.
A bath containing the compound described in No. 44446 may be used as the final bath of the light-sensitive material. If necessary, the stabilizing bath may contain a metal compound such as an ammonium compound, Bi, or Al, a fluorescent whitening agent, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a fungicide, an alkanolamine or a surfactant. Agents can also be added. The water used in the washing or stabilization process includes tap water, deionized water, water that has been sterilized by halogen, an ultraviolet germicidal lamp, and various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use them.
And washing water containing the compounds described in JP-A-5-241309. The temperature and time of the washing or stabilizing bath are preferably 0 to 50 ° C and 5 seconds to 2 minutes.

The processing solution used in the present invention is disclosed in
It is preferable to store in a 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 transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Four steps of a stabilization step may be used instead of the washing step.

A component obtained by removing water from the composition of the developing solution or the fixing solution may be supplied in the form of a solid, dissolved in a predetermined amount of water before use, and used as the developing solution or the fixing solution. Such a treatment agent is called a solid treatment agent. The solid processing agent is
Powders, tablets, granules, powders, lumps or pastes are used, and a preferred form is described in JP-A-61-259921.
No. form or tablet. The method of manufacturing tablets is
For example, JP-A-51-61837 and JP-A-54-15503.
8, No. 52-88025, British Patent 1,213,8
No. 08, No. 08 and the like.
Nos. 109043, 3-39735 and 3-397
It can be produced by a general method described in No. 39 or the like. Furthermore, powder processing agents are described, for example, in JP-A-54-133332.
And British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861.

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

In preparing the solid processing agent, at least two mutually reactive particulate materials among the materials constituting the processing agent are mixed with at least one intervening substance by a substance inert to the reactive substance. It is also possible to adopt a method in which the reactive substance is placed in a layered manner so as to form a layer separated by the separation layer, a bag capable of being vacuum-packaged is used as a packaging material, and the bag is evacuated and sealed. As used herein, the term inert means that the materials do not react under the normal conditions in the package when physically contacted with each other, or that any reaction is not significant. The inert material need only be inert to the two mutually reactive materials, as long as the two reactive materials are inactive in the intended use. Further, an inert substance is a substance used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react in direct contact in a developer, they can be stored in a package for a long time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. Also, by reducing the contact area with sodium hydroxide by briquetting hydroquinone or the like, preservability is improved, and they can be mixed and used. The packaging used for these vacuum packaging materials is bags made from inert plastic films, laminates of plastic material and metal foil.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used. Item The present section 1) Nucleation accelerator A compound of the general formula (I), (II), (III), (IV), (V) or (VI) described in JP-A-6-82943. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) and compound examples II-1 to II-22; Compounds described in JP-A-1-179939. 2) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4, JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Column 20, line 20. Further, spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and JP-A-5-11389. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to line 4 Line 18 in the lower right column of the page. 4) Antifoggants 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, and JP-A 1-237538. Thiosulfinic acid compounds described in the official bulletin. 5) Polymer latex, page 12, lower left column, line 12 to line 20 of JP-A-2-103536. 6) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 7) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column, 15 plasticizer line to page 19, upper right column, line 15 line. 8) Hardener JP-A-2-103536, page 18, upper right column, 5th line to 17th line. 9) Dyes Dyes on page 17, lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 11) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compound A compound represented by the general formula (I) of JP-A-2-301743 (especially compound examples 1 to 50), and a compound represented by the general formula (3) on page 3 to page 20 of JP-A-3-174143. (R-1), (R-2), (R-3), Compound Examples 1 to 75, and the compounds described in JP-A-5-257239 and JP-A-4-278939. 13) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 14) Dihydroxybenze A compound described in the upper left column of page 11 of JP-A-3-39948 to the lower left column of page 12 of JP-A No. 3-39948, and in the publication of EP 452772A.

In the development processing method of the present invention according to claim 1 or 2, the silver halide photographic material preferably contains a hydrazine derivative (hydrazine nucleating agent) in the silver halide emulsion layer. Further, it is more preferable to contain a nucleation accelerator. It is particularly preferable to use a developing solution containing ascorbic acid in the method for developing a silver halide photographic light-sensitive material according to the present invention.

[0105]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 Preparation of Emulsion A 1 solution 1 liter of water 1 liter gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 solutions water 400 ml silver nitrate 100 g 3 solutions water 400 ml Sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachlororhodium (III) (0.001% aqueous solution) 6 ml

Solution 1, Solution 2 and Solution 3 maintained at 40 ° C. and pH 4.5 were simultaneously added over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

After that, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, and 1.0 mg of sodium thiosulfate, 4.0 mg of chloroauric acid, 1.5 mg of triphenylphosphine selenide, 8 mg of sodium benzenethiosulfonate, and 2 mg of sodium benzenethiosulfinate were added. In addition, chemical sensitization was performed at 55 ° C. so as to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene was added, and phenoxyethanol was added as a preservative. Finally, the composition contained 70 mol% of average silver chloride and 0.08 mol% of silver iodide.
A silver iodochlorobromide cubic emulsion A of 0 μm was obtained. (Coefficient of variation of grain size: 10%) Preparation of Emulsion C Except that the time for adding the second and third solutions of Emulsion A and the time for adding the fourth and fifth solutions and the temperature of the first solution were adjusted, the emulsion was prepared in exactly the same manner as Emulsion A. After sensitization, 4-hydroxy-6-methyl-1,
800 mg of 3,3a, 7-tetrazaindene was added, and phenoxyethanol was added as a preservative.
Average silver chloride content 70 mol%, silver iodide 0.08 mol%
A silver iodochlorobromide cubic grain emulsion C having an average grain size of 0.18 μm was obtained. (Coefficient of variation of particle size 12%)

Preparation of non-photosensitive silver halide grains 1 solution water 1 liter gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 solutions water 400 ml silver nitrate 100 g 3 solutions Water 400 ml sodium chloride 13.5 g potassium bromide 45.0 g potassium hexachlororhodate (III) (0.001% aqueous solution) 860 ml

Solution 1, solution 2 and solution 3 maintained at 70 ° C. and pH 4.5 were simultaneously added over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 13.5g Potassium bromide 45.0g

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, the pAg was adjusted to 7.5, phenoxyethanol was added as a preservative, and the mixture finally contained 30 mol% of average silver chloride and 0.08 mol% of silver iodide.
A μm dispersion of unripe silver iodochlorobromide cubic milk particles was obtained. (Coefficient of variation of particle size 10%)

Preparation of non-photosensitive silver halide grains 1 solution 1 liter of water 20 g of gelatin 20 g of sodium chloride 20 g of 1,3-dimethylimidazolidine-2-thione 20 mg 8 mg of sodium benzenethiosulfonate 2 solutions of water 400 ml of silver nitrate 100 g of 3 solutions Water 400ml Potassium bromide 72.0g Potassium hexachlororhodate (III) (0.001% aqueous solution) 2000ml

Solution 1, Solution 2 and Solution 3 maintained at 75 ° C. and pH 4.5 were simultaneously added over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Potassium bromide 72.0g

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, the pAg is adjusted to 7.5, phenoxyethanol is added as a preservative, and finally unripe silver iodobromide cubes having an average particle diameter of 0.5 μm and containing 0.08 mol% of silver iodide. A dispersion of milk particles was obtained. (Coefficient of variation of particle size 10%)

Preparation of Coating Samples 1 to 12 Non-light-sensitive silver halide grains or the amount shown in Table 1 was added to the upper or lower layer of the protective layer, and the UL layer, emulsion layer, and protective layer Coating samples 1 to 12 were prepared by coating the lower layer and the upper layer of the protective layer.

Emulsion layer Sensitizing dye (1) was added to emulsion A at 5.7 × 10 ^-4 mol / mol Ag.
Was added for spectral sensitization. Furthermore, KBr 3.4 × 10
^-4 mol / mol Ag, compound (1) 3.2 × 10 ^-4 mol / mol Ag, compound (2) 8.0 × 10 ^-4 mol / mol Ag,
Hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound (3)
5 × 10 ⁻⁴ mol / mol Ag, compound (4) was 6.0 × 10
^-4 mol / mol Ag, polyethyl acrylate latex and 0.01 μm colloidal silica in an amount corresponding to a gelatin binder ratio of 30% each, aqueous latex compound (5) at 100 mg / m ² , and a dispersion of polyethyl acrylate. 150 mg / m ² , a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (weight ratio: 88: 5: 7) was added to 1
50 mg / m ² , core-shell latex (core: styrene / butadiene copolymer (weight ratio 37/63), shell: styrene / 2-acetoxyethyl methacrylate (weight ratio 84/16), core / shell ratio = 50/50 )
To 150 mg / m ² , 100 g of gelatin
(6) was added, and the pH of the solution was adjusted to 5.5 using citric acid to prepare an emulsion coating liquid a. Emulsion C was prepared in exactly the same manner as Emulsion Coating Solution a except that Emulsion C was used instead of Emulsion A and no sensitizing dye (1) was added. Emulsion a and emulsion c were mixed at a silver amount ratio of 1: 3, and a silver coating amount of 3.0 g / m ² and a gelatin coating amount of 1 were applied to an undercoated polyester support having a moisture-proof layer containing vinylidene chloride. 0.3 g / m ² . Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Non-photosensitive silver halide grains or amount in Table 1 Compound (7) (gelatin dispersion) 20 mg / m ² Particle size 10 Colloidal silica having a thickness of 〜20 μm 30 mg / m ² Compound (8) 50 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (9) 20 mg / m ² Underlayer of protective layer Gelatin 0.5 g / m ² Non-photosensitive silver halide Particle or amount in Table 1 Compound (10) 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (6) 40 mg / m ² Compound (11) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Compound (12) 40 mg / m ² Compound (13) 20 mg / m ² Compound (14) 90 mg / m ² Compound (15) 40 mg / m ² Compound (16) 26 mg / m ² 1 2,3-divinylsulfonyl-2-propanol 60 mg / m ² Fine particles of polymethyl methacrylate (average particle size 6.5 μm) 30 mg / m ² Liquid paraffin 78 mg / m ² Compound (6) 120 mg / m ² Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ²

[0118]

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[0119]

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[0120]

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The obtained sample was subjected to 80% flat screen exposure using an image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd. The developer No. of Table-2. Using LDT-1060 manufactured by Dainippon Screen Co., Ltd., developing was performed at 35 ° C. for 30 seconds, followed by fixing, washing and drying. The exposure unevenness of the obtained sample was evaluated by five-grade evaluation (5 is the best, 1 is the worst).

[0122]

[Table 1]

<Results> As shown in Table 1, the samples having a hydrophilic colloid layer containing the non-photosensitive silver halide grains of the present invention showed little exposure unevenness.

Example 2 The change in photographic properties and the silver stain due to the running test were evaluated using the coating sample No. 1 in Table 1 of Example 1. 1 to 5 were evaluated. The running conditions were such that 100 rounds of a film of large paper size (50.8 cm × 61.0 cm) half-exposed for one day were processed, running for six days and resting for one day were performed as one round for six rounds. The automatic processing was performed using FG-680A manufactured by Fuji Photo Film Co., Ltd. at 35 ° C. and 30 ″ (development time).

The compositions of the developing solution and the fixing solution are shown below. (Developer composition) Potassium hydroxide 105.0 g Diethylenetriamine-pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.24 g 4- Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.35 g 2-mercaptobenzimidazole-5-sulfonic acid sodium 0.432 g sodium erythorbate 9.0 g diethylene glycol 60.0 g Potassium hydroxide was added, and water was added. Add 1 liter and adjust the pH to 10.7. 1 liter

A replenisher for test as shown in Table 2 was prepared by using a replenisher obtained by adding water 2 to the above concentrated solution 1. As the mother liquor, a liquid obtained by adding 333 ml of water per liter of the liquid shown in Table 2 was used.

[0127]

[Table 2]

(Formulation of Fixing Solution) Ammonium thiosulfate 360.0 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 3 liters by adding water The replenishment rate of the fixing solution was 260 ml / m ² .

The photographic properties were evaluated as follows. The exposure was performed with a xenon flash light having an emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 633 nm. As an index (gradation) indicating the contrast of the image, the point of fog + density of 0.1 on the characteristic curve is connected by a straight line from the point of fog + density of 3.0,
The slope of this straight line was represented as a gamma value. That is, gamma (gradation) = (3.0-0.1) / [log (exposure amount giving density 3.0)-(exposure amount giving density 0.1)]. This indicates that the photographic characteristics are high. As a photographic material for graphic arts, gamma is preferably 10 or more, more preferably 15 or more. The sensitivity was expressed as a relative value after running, with the reciprocal of the amount of exposure required to obtain a density of 1.5 when each sample was treated with a new solution taken as 100. The relative value is desirably 95 to 105.

The silver stain after running was visually evaluated on a scale of 1 to 5. A state in which no silver stain is generated on the film, the developing tank, and the roller is denoted by “5”, and a state in which silver is generated on the entire surface of the film and a large amount of silver is generated on the developing tank and the roller is denoted by “1”. " “4” is not generated in the film, but is slightly generated in the developing tank and the roller, but is at a practically acceptable level. "3" and below are practically problematic or unacceptable. Table 3 shows sample N
The results of o, developer No., replenishment amount, photographic change after running and silver stain are shown.

[0131]

[Table 3]

As is clear from Table 3, when the compound of the general formula (I) of the present invention is used with the light-sensitive material of the present invention, no silver stain is generated without impairing the photographic properties even in a small replenishing amount. I understand that.

Example 3 Instead of using the imagesetter FT-R5055 manufactured by Dainippon Screen Co., Ltd. in Example 1, a select set 5000 manufactured by Agfagewald Co., Ltd., Avantra 2
5, or AccuSet 1000, Dreb 800 manufactured by Cytex Corporation, Rhino 6 manufactured by Heidel Corporation
30, Quasar, Hercules Elite, or Signa Setter, Lux Setter RC-5600V manufactured by Fuji Photo Film Co., Ltd., or Laxel F-900
0 or any one of Panther Pro 62 manufactured by Prepress Co., Ltd.
2 was subjected to flat screen exposure of 80% and subjected to development processing. As a result, the sample having the hydrophilic colloid layer containing the non-photosensitive silver halide grains of the present invention showed little exposure unevenness.

Example 4 Preparation of Coated Sample When preparing the emulsion coating solution a of Example 1, a sensitizing dye (SD-2) was used instead of the sensitizing dye (SD-1) at 0.7 × 10 ^-4 mol / mol. Mol Ag, sensitizing dye (SD-3) at 2.3 × 10 ^-4 mol / mol A
A sample was prepared in the same manner as in Example 1 except that g was added.

[0135]

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(1) Exposure and development treatment The above sample was passed through an interference filter having a peak at 488 nm and passed through a step wedge to emit light for 10 ^-6 sec.
The sample was exposed to xenon flash light of c.

The method for producing a solid developer is as follows. A container made of high-density polyethylene (average wall thickness = 500 μm, partially 200 to 1000 μm) is packed with developing components corresponding to 10 liters of a working liquid as a solid. Was. At this time, each component was mixed and then charged into a container.

Next, the composition of the developer is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 71.8 g Sodium sulfite (raw powder) 35.0 g Potassium carbonate (raw powder) 62.0 g Hydroquinone (briquette) 40.0 g Briquette diethylenetriaminepentaacetic acid 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl 1.50 g -1-phenyl-3-pyrazolidone 2-mercaptobenzimidazole 0.30 g -5-sodium sulfonate erythorbic acid Sodium 6.0 g Potassium bromide 6.6 g 3- (5-Mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g Based on this formulation, the compounds in Table 2 were added to prepare a test developer. The pH of this test developer when water was added to make it 1 liter was 10.65, and this was used as a mother liquor, and the pH when water was added to make it 1.17 liter was 10.61. This was used as a replenisher.

Here, the raw material was used in the form of a raw, general industrial product, and the alkali metal salt beads were commercially available. If the raw material is in the form of briquettes, pressurize and compress it using a briquetting machine, and make it amorphous
A rugby ball type shape of about 6 mm was prepared, crushed and used. For the minor components, each component was blended before briquetting.

The fixing solution was prepared by using the following formulation in both a solid part and a liquid part by high density polyethylene (thickness average = 500 μm,
What was filled in a container having a width of 200 to 1000 μm) was used. The solution volume after dissolution was 10 liters, and pH =
4.85. Fixer replenishment rate is 260 ml / m ²
Met.

<Solid agent part> Ammonium thiosulfate 1300 g Sodium acetate 400 g Sodium metabisulfite 200 g <Liquid agent part> Aluminum sulfate (27%) 300 g Sulfuric acid (75%) 30 g Sodium gluconate 20 g EDTA 0.3 g Tartaric acid 30 g It is mixed and filled.

Evaluation of exposure unevenness (image setter used was CELIC-8200 manufactured by Fuji Film Co., Ltd.), photographic properties and running properties were evaluated in the same manner as in Examples 1 and 2. as a result,
The same results as in Examples 1 and 2 were obtained.

[0143]

The photosensitive material of the present invention hardly causes unevenness even when exposed by an image setter, and has a stable developing property of less than pH 11.0 by using a developing solution using the compound of the general formula (I) of the present invention. Even if the replenishing amount was reduced with the liquid, the variation in photographic properties was small, the generation of silver stain was small, and a silver halide black-and-white photographic light-sensitive material capable of always obtaining stable photographic performance was obtained.

Claims (2)

[Claims] 1. The same or different silver halide emulsion layers provided on a support contain at least two silver halide emulsions having different sensitivities, and at least two silver halide emulsion layers other than the silver halide emulsion layers are provided. A method for developing a silver halide photographic material in which one hydrophilic colloid layer contains at least one kind of non-photosensitive silver halide grains, comprising a compound represented by the following formula (I) and having a pH of 9: 0.0-1
The replenishment amount of the developer is 323 with the developer being 1.0.
A method for developing a black-and-white silver halide photographic light-sensitive material, wherein a continuous development processing is carried out at a flow rate of at most ml / m ² . General formula (I) In the formula, R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. However, R ₁ and R ₃ do not represent a hydroxy group. R _{1 to} R ₄ may be the same or different, and at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group. 2. The method according to claim 1, wherein the developer is prepared using a solid processing agent.