JPH10153838A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method capable of obtaining photographic characteristics high in sensitivity and contrast without causing silver sludge in development processing by processing the photosensitive material having a specified silver chloride content or more in a silver halide emulsion layer in the presence of specified compound. SOLUTION: The silver halide photographic sensitive material has the silver halide emulsion layer having the silver chloride compound of >=70mol% and comprising silver halide grains each having a surface layer of a localized layer on the surface less in the silver chloride content, and this photosensitive material is developed and processed in the presence of the compound represented by the formula in which each of D and E is a -CH= or -(Ro )= group of an N atom; Ro is a substituent; each of L1 -L3 is an H or halogen atom or an optional substituent combined through a C atom with the ring; at least one of L1 , L2 , L3 and R0 is a -SM group; and M is an alkali metal or H atom or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic material. In particular, the present invention relates to a method for preventing silver sludge in a developing process of a black-and-white photographic light-sensitive material for printing.

[0002]

2. Description of the Related Art Generally, in the development processing of photosensitive materials,
From the viewpoints of speed, simplicity, and handling, an automatic developing machine (hereinafter referred to as an automatic developing machine) is often used.
In recent years, the demand for low replenishment and speeding up of development processing has been increasing, but to meet these demands,
One measure is to increase the activity of the developer. In the processing of black-and-white photosensitive materials, the activity can be increased by increasing the concentration of the developing agent, but the deterioration due to air oxidation is remarkable.
Also, reducing the thickness of the photosensitive material (for example, the protective layer) is effective for rapid processing.

[0003] By the way, the use of a sulfite to prevent the deterioration of a developer has been known for a long time. However, since it has a dissolving action of silver halide, silver is eluted from the photosensitive material as a silver sulfite complex into the developer. Would. The silver complex is reduced in the developing solution and gradually adheres and accumulates on the developing tank and the roller. This is referred to as silver stain or silver sludge, which adheres to the photographic material to be processed, thereby contaminating the image or contaminating the self-developing machine itself. Therefore, it is necessary to periodically clean and maintain the equipment.

As described in JP-A-56-24347 and JP-A-8-6215, methods for reducing such silver stains include reducing silver ions eluted into a developer and / or reducing silver ions. A method of adding a compound that suppresses the reduction of ions to silver is known. However, in order to obtain a sufficient silver stain prevention effect with these materials, it is necessary to increase the amount of the former compound to be added, which greatly affects photographic properties such as lowering sensitivity and increasing fog.
These adverse effects are particularly remarkable in a super-high contrast material containing a hydrazine compound. In the case of the latter compound, since the so-called reduction suppression ability is high, it is certainly effective in preventing dirt on the racks and tanks of the automatic processing machine. Since the suppression of reduction at a locally high silver concentration portion is insufficient, reduced silver precipitates on the roller and adheres to the light-sensitive material to become silver stain.

On the other hand, in a silver halide photographic material requiring a rapid development step, a silver chlorobromide emulsion having good developability is used as a silver halide emulsion constituting the light-sensitive material. It is known that the use of a silver chlorobromide emulsion having a high silver chloride content yields a photosensitive material having better developability. However, such a silver chlorobromide emulsion having a high silver chloride content has a low sensitivity particularly at high illuminance and short-time exposure, and further has a high solubility. Was a problem.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-sensitivity, high-contrast photographic property and to prevent silver sludge in the development processing of a light-sensitive material.

[0007]

The object of the present invention is to provide a silver halide grain having a silver chloride content of 70 mol% or more on a support, and a surface layer having a silver chloride content less than that of the interior. And / or a silver halide photographic material having at least one silver halide emulsion layer composed of silver halide grains having a localized phase having a smaller silver chloride content on the surface than the inside, This has been attained by a method for processing a silver halide light-sensitive material, which comprises developing in the presence of at least one of the compounds represented by the formula (I). General formula (I)

[0008]

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In the general formula (I), D and E represent -CH =
Group, —C (R ₀ ) = group or a nitrogen atom, wherein R
₀ represents a substituent. L ₁ , L ₂ , and L ₃ represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring at any of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and L _{1 to} L ₃ May be the same or different. Provided that at least one of L ₁ , L ₂ , L ₃ and R ₀ is
—SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group). When E and D represent one nitrogen atom and one carbon atom, E represents a nitrogen atom and D represents a carbon atom (-CH = group or -C ( _R0 ) = group). ₂ and L ₃ do not represent a hydroxy group.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the formula (I) will be described below in detail. In the general formula (I), D, E
Represents a —CH ＝ group, a —C (R ₀ ) ＝ group, or a nitrogen atom, wherein R ₀ represents a substituent. L ₁ , L ₂ , and L ₃ represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring at any of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and L _{1 to} L ₃ May be the same or different. However, at least one of L ₁ , L ₂ , L ₃ and R ₀ represents a —SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group). When E and D represent one nitrogen atom and one carbon atom, E is a nitrogen atom and D
Represents a carbon atom (—CH ＝ group or —C (R ₀ ) ＝ group), in which case L ₂ and L ₃ do not represent a hydroxy group. Specific examples of the substituent represented by L ₁ , L ₂ , and L ₃ and the substituent represented by R ₀ include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), Alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing quaternized nitrogen atom (eg, pyridinio group), acyl Group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group,
A hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit),
Aryloxy, heterocyclic oxy, acyloxy, (alkoxy or aryloxy) carbonyloxy, carbamoyloxy, sulfonyloxy, amino, (alkyl, aryl or heterocycle)
An amino group, a hydroxyamino group, an N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, an acylamino group, a sulfonamide group, a ureido group, a thioureido group, an 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, acyl Sulfamoylamino group, nitro group, mercapto group,
(Alkyl, aryl or heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof , A group containing a phosphoric amide or a phosphoric ester structure, and the like. These substituents may be further substituted with these substituents. Incidentally, E is D is a carbon atom by a nitrogen atom (-CH = group or -C (R ₀₎ = group) for representing, never L _2, L ₃ represents a hydroxy group.

The substituent represented by L ₁ , L ₂ , L ₃ and the substituent represented by R ₀ are more preferably a substituent having ₀ to 15 carbon atoms, such as a chloro atom, an alkyl group, an aryl group. 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 hetero ring)
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,
An aryl or heterocycle) thio group, a sulfo group or a salt thereof, or a sulfamoyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a carbamoyl group or a salt thereof, an alkoxy group, 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, A thioureido group, a sulfamoylamino group, a mercapto group, a (alkyl, aryl, or heterocyclic) thio group, a sulfo group or a salt thereof, and most preferably an amino group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group , Alkylamino group, arylamino group, alkyl Thio, a Aruruchio group, a mercapto group, a carboxy group or a salt thereof, a sulfo group or a salt thereof. In the general formula (I), L ₁ , L ₂ , L ₃ and R ₀ may combine with each other to form a condensed ring in which a hydrocarbon ring, a hetero ring or an aromatic ring is condensed.

In the general formula (I), M represents an alkali metal atom, a hydrogen atom or an ammonium group. Here specifically the alkali metal atom is Na, K, Li, Mg, Ca, etc., they -S ^- present as a counter cation.
M is preferably a hydrogen atom, an ammonium group, Na
⁺ Or K ⁺ , and particularly preferably a hydrogen atom. Among the compounds of the general formula (I), the following general formula (A):
The compound represented by (B) is preferred.

[0013]

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Next, the general formula (A) will be described in detail. R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, or any substituent bonded to a ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, which is represented by L _{1 in the} general formula (I). , L ₂ and L ₃ are the same as defined above, and the preferred range is also the same. 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.

In the general formula (A), at least one of R _{1 to} R ₄ is a —SM group, more preferably R _{1 to} R 4.
_At least two of ₄ are -SM groups. When at least two of R _{1 to} R ₄ are —SM groups, preferably, R ₄ and R ₁ , or R ₄ and R ₃ are —SM groups.

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

[0017]

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In the general formula (A-1), R_TenIs a mercapto
X represents a water-soluble group, a hydrogen atom, or an optional substituent;
Represents a substituent substituted with a group or a water-soluble group. one
Y in the general formula (A-2)₁Is a water-soluble group or a water-soluble group
Represents a substituted substituent; ₂₀Is a hydrogen atom or any
Represents a substituent. In the general formula (A-3), Y_TwoIs also a water-soluble group
Or a substituent substituted with a water-soluble group;₃₀Is hydrogen
Represents an atom or an optional substituent. Where R_TenAnd Y₁
Does not represent a hydroxy group.

Next, the compounds represented by formulas (A-1) to (A-3) will be described in detail. In the general formula (A-1), R ₁₀ represents a mercapto group, a hydrogen atom or an arbitrary substituent. Here, the optional substituent means R in the general formula (A)
It may be the same as those described for ₁ to R _4. R ₁₀ is preferably a mercapto group, a hydrogen atom,
Or a group selected from the following substituents having 0 to 15 carbon atoms. That is, examples include 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, and an arylamino group. In the general formula (A-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 ammonio group, 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 is a methyl group substituted by two electron-withdrawing groups, specifically, dicyanomethyl,
and groups such as α-cyano-α-ethoxycarbonylmethyl and α-acetyl-α-ethoxycarbonylmethyl. The substituent represented by X in the general formula (A-1) is the above-mentioned water-soluble group or a substituent substituted with the above-mentioned water-soluble group, and the substituent has 0 to 15 carbon atoms. With a substituent of
Alkyl group, aryl group, heterocyclic group, alkoxy group,
Aryloxy group, heterocyclic oxy group, acyloxy group, (alkyl, aryl or heterocyclic) amino group,
Acylamino group, sulfonamide group, ureido group, thioureido group, imide group, sulfamoylamino group, (alkyl, aryl or heterocycle) thio group, (alkyl, aryl) sulfonyl group, sulfamoyl group, amino group and the like. 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, an (alkyl, aryl or heterocycle) amino group, an (alkyl, aryl or (Heterocycle) a group such as a thio group.

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

[0021]

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Where R₁₁Is R of the general formula (A-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 preferable.
As water-soluble groups, especially sulfo groups (or their salts),
A ruboxyl group (or a salt thereof), a hydroxy group,
A mino group is preferred. R₁₂And R₁₃Is an alkyl group or
When representing an aryl group, these are bonded to each other to form a cyclic structure.
The structure may be formed. In addition, due to the cyclic structure,
It may form a terrorist ring.

In the general formula (A-2), Y₁Is a water-soluble group
Or a substituent substituted with a water-soluble group, and represented by the general formula (A-1)
X is synonymous. Y in the general formula (A-2)₁Represented by
Water-soluble group or a substituent substituted with a water-soluble group
More preferably, it is substituted with an active methine group or a water-soluble group.
The following substituted groups: amino group, alkoxy group,
Oxy, alkylthio, arylthio, alk
A kill group and an aryl group. Y₁More preferred as
Is substituted with an active methine group or a water-soluble group (Al
A kill, aryl, or heterocycle) amino group;
Here, the water-soluble group includes a hydroxy group, a carboxy group and the like.
Or a salt thereof, a sulfo group or a salt thereof is particularly preferred. Y
₁Particularly preferably as a hydroxy group, a carboxy group
(Or its salt) or sulfo group (or its salt)
Substituted (alkyl, aryl, or heterocycle)
An amino group, and -N (R₀₁) (R₀₂) Group. This
Here R₀₁, R ₀₂Is R of the general formula (1-a)₁₂,
R₁₃And the preferred range is also the same.
is there.

In the general formula (A-2), R ₂₀ represents a hydrogen atom or an arbitrary substituent, wherein the optional substituent is the same as those described for R _{1 to} R _{4 in} the general formula (A). The same is given. R ₂₀ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms. That is, a hydroxy group, an amino group, an alkyl group,
Examples thereof include 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 (A-3), Y_TwoIs a water-soluble group
Or a substituent substituted with a water-soluble group,₃₀Is hydrogen field
Represents a child or an optional substituent. In general formula (A-3)
Y _Two, R₃₀Is Y in the general formula (A-2)₁, The general formula (A
-2) R₂₀And the preferred range is also
Is the same.

Next, the general formula (B) will be described in detail. R _{5 to} R ₇ in the general formula (B) have the same meanings as R _{1 to} R _{4 in} the general formula (A), and their preferred ranges are also the same. Among the compounds represented by the general formula (B), the compound represented by the general formula (B-1) is particularly preferable.

[0027]

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In the general formula (B-1), R ₅₀ has the same meaning as R _{5 to} R _{7 in} the general formula (B), and more preferably, X in the general formulas (A-1) to (A-3) It is a water-soluble group as defined for Y ₁ and Y ₂ or a group substituted with a water-soluble group. Furthermore, the general formula (B
-1) is most preferably a compound of the general formula (B-1-
It is a compound represented by a).

[0029]

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In the general formula (B-1-a), R₅₁, R₅₂
Is R of the general formula (A-1-a)₁₂, R ₁₃A group equivalent to
The preferred range is 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.

[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.

The silver halide grains of the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention are obtained by laminating one or more surface layers having a different halogen composition from the silver halide constituting the inside of the grain. And / or silver halide grains having a localized phase different from the inside on the surface. The silver halide of the grains is silver chlorobromide,
Any of silver chloroiodobromide may be used, but the average silver chloride content of the whole grains is 70 mol% or more, preferably 80 mol%.
That is all. The silver halide inside the grains has a constant halogen composition, preferably silver chlorobromide, silver chloroiodobromide or silver chloride having a silver chloride content of 85 mol% or more. The silver halide in the localized layer on the surface layer or surface of the grains is silver chlorobromide or silver chloroiodobromide having a smaller silver chloride content than the internal halogen composition, and the silver chloride content is constant. May also change continuously toward the particle surface. The difference in silver chloride content between the inner and surface layers or the localized phase on the inner and surface layers is preferably at least 5 mol%, more preferably at least 10 mol%. The volume of the surface layer is 5 to 5 times that of the silver halide grains.
Preferably occupy 50%, more preferably 5-30%,
The volume of the localized phase on the surface is preferably 10 mol% or less. The shapes of silver halide grains are cubic, tetrahedral, octahedral,
Any of an irregular shape and a plate shape may be used, but a cube is preferable. The average grain size of the silver halide is preferably 0.5 μm or less, more preferably 0.1 to 0.4 μm, and a variation represented by {(standard deviation of grain size) / (average grain size)} × 100. Those having a narrow particle size distribution having a coefficient of 15% or less, more preferably 10% or less are preferred. The photographic emulsion used in the present invention is
Chimie et Physique Photographique by P. Glafkides
(Paul Montel, 1967), Photograp by GF Dufin
hic EmulsionChemistry (The Forcal Press, 1966
Year), Making and Coating Pho by VL Zelikman et al
It can be prepared using a method described in, for example, tographic Emulsion (The Forcal Press, 1964).

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 tetrasubstituted thiourea compounds, and JP-A-53-82408 and JP-A-5-82408.
It is described in 5-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent varies depending on the type of the compound used, the target grain size, and the halogen composition.
It is preferably from 0 ^-5 to 10 ^-2 mol.

According to the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to produce 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. In order to make the particle size uniform, British Patent No. 1,535,016, Japanese Patent Publication No. 48-3
6890, 52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and British Patent No. 4,242,445, JP-A-55-1
It is preferable to use the method of changing the concentration of the aqueous solution as described in No. 58124 to grow the solution quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. Is preferred. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, more preferably in the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in silver halide grains, and are disclosed in JP-A-63-29603 and JP-A-2-30623.
No. 6, No. 3-175545, No. 4-76534, No. 6-110146, Japanese Patent Application No. 4-
As described in 68305 and the like, it can be contained in the particles with a distribution.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III)
Complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, trizalatrodium (III) complex salts and the like can be mentioned. These rhodium compounds are used by dissolving them in water or a suitable solvent.
That is, a method of adding an aqueous solution of hydrogen halide (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 5 × 10 ^-6 mol, particularly preferably 5 × 10 ^-8 mol to 1 × 1 mol per mol of silver halide.
0 ^-6 mol. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. .

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and JP-A-1-285941.
, 2-20852, 2-20855, etc. in the form of a water-soluble complex salt. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ^-n where M represents Ru, Re or Os, 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 (H ₂ O)] ^-2 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)) ^-2 [Ru (CN) ₆ ] ^-4 [Ru (CO) ₃ Cl ₃ ] ^-2 [Ru (CO) Cl ₅ ] ^-2 [Ru (CO) Br ₅ ] ^-2 [OsCl ₆ ] ^-3 [OsCl ₅ (NO)] ^-2 [Os (NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN ) ₄ ) ^-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. The addition of these compounds was
At the time of manufacture of the emulsion and at each stage before coating the emulsion.
Can be carried out.
It is preferably incorporated into silver halide grains. these
The compound is added during silver halide grain formation to
For incorporation into silver halide particles, powder of metal complex or Na
The aqueous solution dissolved together with Cl and KCl is
Method to be added to a neutral salt or a water-soluble halide solution,
Or when silver salt and halide solution are mixed at the same time,
3 as a solution of 3
How to prepare silver halide grains or the amount required during grain formation
Of an aqueous solution of the metal complex of
You. In particular, water soluble in powder or dissolved with NaCl, KCl
A preferred method is to add the solution to a water-soluble halide solution.
To add to the particle surface, immediately after particle formation or physical ripening
The required amount of metal during or at the end or during chemical ripening
An aqueous solution of the complex can also be charged to the reaction vessel.

As the iridium compound used in the present invention, various compounds can be used. Examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, and hexacyanoiridium.
These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or alkali halides (eg KCl, NaC
l, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another iridium-doped silver halide grain during silver halide preparation.

The silver halide grains in the present invention may be doped with another heavy metal salt. In particular, doping of an Fe salt such as K ₄ [Fe (CN) ₆ ] is advantageously performed. Further, the silver halide grains used in the present invention may contain metal atoms such as cobalt, nickel, palladium, platinum, gold, thallium, copper, lead, and chromium. The amount of the metal is preferably 1 × 10 ^-9 to 1 × 10 ^-4 mol per mol of silver halide. Further, in order to incorporate the metal, a metal salt in the form of a single salt, a double salt, or a complex salt can be added at the time of preparing particles.

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. Unstable selenium compounds include JP-B-44-15748, JP-B-43-13489, and JP-A-2-13097.
Compounds described in 2-229300, 3-21798 and the like can be used. In particular, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compound represented by (IX).

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. Regarding the formation rate of silver telluride in silver halide emulsion
It can be tested by the method described in No. 6739. Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, and 3,771
No. 2,031, British Patent No. 235,211 and No. 1,121,496, No. 1,
No. 295,462, No. 1,396,696, Canadian Patent No. 800,958,
Japanese Patent Application Nos. 2-333819, 3-53693, 3-31598, 4-1297
No. 87, Journal of Chemical Society
Chemical Communication (J.Chem.Soc.Chem.Comm
un.) 635 (1980), Ibid 1102 (1979), Ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin. Trans.) 1,21
91 (1980), edited by S. Patai, edited by The Chemistry
The Chemistry of Organic Serenium
and Tellunium Compounds), Vol 1 (1986), Vol 2 (198
The compound described in 7) can be used. Especially Japanese Patent Application 4-
Compounds represented by general formulas (II), (III) and (IV) in 146739 are preferred.

[0052] The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, 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. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in European Patent Publication EP293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (e.g., those having different average grain sizes, different halogen compositions, different crystal habits, different chemical habits, Those with different conditions) may be used in combination.

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 are described in, for example, RESEARCH DISCLOSURE Item 17643 IV-A (December 1978, p. 23) and Item 1831X (August 1979, p. 437) or cited in the literature. Have been. 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 to Example1 to Example
Compound No. 14; compounds Nos. 1 to 7 described in West German Patent 936,071; B) For helium-neon laser light source, I-1 to I described in JP-A-54-18726.
-38 compound, I- described in JP-A-6-75322.
Compounds from 1 to I-35 and JP-A-7-287338
Compounds I-1 to I-34 described in JP-A-55-39818 (C).
To 20, described in JP-A-62-284343.
To I-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 of I-1 to I-37 described in JP-A-59-191332. -12 compound, JP-A-60-8084
Compounds of I-1 to I-22 described in No. 1;
Compounds I-1 to I-29 described in JP-A-335342 and I-1 to I-29 described in JP-A-59-192242.
-18 compound, E) for tungsten and xenon light sources of a plate making camera, compounds (1) to (19) represented by general formula [I] described in JP-A-55-45015; No. 7-346193, I-1 to I-9
Compound 7 and 4 described in JP-A-6-242547.
A compound of -A to 4-S, a compound of 5-A to 5-Q,
Compounds such as 6-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 Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section IV on page IV, or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding 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 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye using a compound that causes red shift and adding the solution 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. Pat. 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 silver halide grain forming step and / or before the desalting, during the desilvering step and / or after the 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 the 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, etc. 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 hydrazine derivative used in the present invention is
Compounds represented by the following general formula (N) are preferred. General formula (N)

[0059]

Embedded image

Where R₂₀Is an aliphatic group, an aromatic group, or
R represents a heterocyclic group;_TenRepresents a hydrogen atom or a blocking group
Represents, G_TenIs -CO-, -COCO-, -C = S-,-
SO _Two-, -SO-, -PO (R₃₀) -Group (R₃₀Is R_Ten
Selected from the same range as the group defined in_TenDifferent from
May be. ) Or iminomethylene group.
A _Ten, A₂₀Are both hydrogen atoms, or one is a hydrogen atom
And the other is a substituted or unsubstituted alkylsulfonyl group,
Or a substituted or unsubstituted arylsulfonyl group,
Or a substituted or unsubstituted acyl group.

In the general formula (N), the aliphatic group represented by R ₂₀ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. . In the general formula (N), R
_The aromatic group represented by ₂₀ is a monocyclic or condensed-ring aryl group, such as a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₂₀ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, for example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, Examples include a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a piperidine ring, and a triazine ring. Preferred as R ₂₀ is an aryl group, and particularly preferred is a phenyl group.

R ₂₀ may be substituted. Representative examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group, an active methine group). A alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group,
Aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group ( (Including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, (Alkyl, aryl, or heterocyclic) amino group, N-substituted 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 ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, A nitro group, a mercapto group, an (alkyl, aryl, or heterocyclic) thio group, an (alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group,
An acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group having a phosphoric amide or a phosphoric ester structure, and the like can be given.

These substituents may be further substituted with these substituents.

The substituent which R ₂₀ may have is preferably an alkyl group having 1 to 20 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group,
Acylamino group, sulfonamide group, ureido group, sulfamoylamino group, imide group, thioureido group, phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl Group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocyclic) thio group, sulfo group (including its salt), sulfamoyl group, halogen atom, cyano group, nitro group and the like. .

In the general formula (N), R ₁₀ represents a hydrogen atom or a block group, and the block group is specifically an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group.

The alkyl group represented by R ₁₀ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, a trifluoromethyl group, a difluoromethyl group,
-Carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, o-hydroxybenzyl group and the like. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and examples thereof include a vinyl group, 2-ethoxycarbonylvinyl group, and 2-trifluoro-2-methoxycarbonylvinyl group. The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed-ring aryl group is preferable, and an aryl group containing a benzene ring is particularly preferable. For example, a phenyl group, a 3,5-dichlorophenyl group,
Examples include a 2-methanesulfonamidophenyl group, a 2-carbamoylphenyl group, a 4-cyanophenyl group, and a 2-hydroxymethylphenyl group. The heterocyclic group is preferably a 5- to 6-membered, saturated or unsaturated, monocyclic or fused-ring heterocyclic group containing at least one nitrogen, oxygen and sulfur atom, such as a morpholino group, a piperidino group (N -Substituted), imidazolyl group, indazolyl group (such as 4-nitroindazolyl group), pyrazolyl group,
Examples include a triazolyl group, a benzimidazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group (such as an N-methyl-3-pyridinio group), a quinolinio group, and a quinolyl group.
Morpholino, piperidino, pyridyl, pyridinio, indazolyl and the like are particularly preferred.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, such as a methoxy group, a 2-hydroxyethoxy group and a benzyloxy group. As the aryloxy group, a phenoxy group is preferable, and as the amino group, an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized (Including a nitrogen-containing heterocyclic group containing a nitrogen atom). Examples of the amino group include 2,2,6,6-tetramethylpiperidine-
4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-
And a 3-pyridinioamino group. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (such as a 4-benzenesulfonamidophenylhydrazino group) is particularly preferred.

The group represented by R ₁₀ may be substituted. Preferred examples of the substituent include those exemplified as the substituent of R ₂₀ .

In the general formula (N), R_TenIs G_Ten-R_Tenof
The part is split from the residual molecule, -G _Ten-R_TenPart atom
Cyclization reaction that produces a cyclic structure containing
And examples thereof include, for example,
And those described in JP-A-3-29751.

The hydrazine derivative represented by the general formula (N) may incorporate an adsorptive group that adsorbs to silver halide. Examples of such an adsorbing group include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercapto heterocyclic groups, and triazole groups, which are described in U.S. Pat. Nos. 195233, 59-200231, 59-201045, 59-201046, and 5
Nos. 9-201047, 59-201048, 59
-201049, JP-A-61-170733, and 6
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285
No. 344.

R ₁₀ or R _{20 in} the general formula (N) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁₀ or R ₂₀ in the general formula (N) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (N) is a polymer having a hydrazino group. Represents, for example, JP-A-64-86134
No., JP-A-4-16938, JP-A-5-97091, WO95-32452, WO95-32453, Japanese Patent Application No. 7-3511
No. 32, Japanese Patent Application No. 7-351269, Japanese Patent Application No. 7-351168, Japanese Patent Application No. 7-351
Compounds described in Japanese Patent Application No. 351287 and Japanese Patent Application No. 7-351279 are exemplified.

In the general formula (N), R ₁₀ or R ₂₀ represents a cationic group (specifically, a group containing a quaternary ammonium group, or a nitrogen-containing group containing a quaternized nitrogen atom). A group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, (alkyl, aryl,
Or a heterocycle) thio group, or a dissociable group (such as a carboxy group, a sulfo group, an acylsulfamoyl group, or a carbamoylsulfamoyl group) that can be dissociated by a base. Examples of these groups include, for example, JP-A-7-234471 and JP-A-5-333466.
JP-A-6-19032, JP-A-6-19031
JP-A-5-45761, U.S. Pat. No. 4,994,365.
No. 4,988,604, JP-A-73-2592.
No. 40, JP-A-7-5610, JP-A-7-24434
No. 8, German Patent No. 4006032 and the like.

In the general formula (N), A ₁₀ and A ₂₀ represent a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group or a Hammett having a sum of substituent constants of -0.5. A phenylsulfonyl group substituted as described above), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; Alternatively, a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (here, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group. ))). A ₁₀ and A ₂₀ are most preferably a hydrogen atom.

Next, in the present invention, particularly preferred hydrazine derivatives will be described. R ₂₀ is particularly preferably a substituted phenyl group, a ballast group via a sulfonamide group, an acylamino group, a ureido group, or a carbamoyl group, an adsorptive group to silver halide, a group containing a quaternary ammonium group,
A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, a group containing a repeating unit of an ethyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, a group capable of dissociating in an alkaline developing solution (carboxy) Group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.) or a hydrazino group capable of forming a multimer (-N
It is preferable that at least one group represented by) at HNH-G ₁₀ -R ₁₀ have been substituted. R ₂₀ is most preferably a phenyl group substituted with a benzenesulfonamide group,
As the substituent on the benzene ring of the benzenesulfonamide group, it is preferable to have any one of the above groups directly or via a linking group.

Among the groups represented by R ₁₀ , when G ₁₀ is a —CO— group, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group is preferable. Preferred are a hydrogen atom, an alkyl group, and a substituted aryl group (an electron-withdrawing group or an o-hydroxymethyl group is particularly preferred as the substituent).
Most preferably, it is an alkyl group. G ₁₀ is -COCO-
In the case of a group, an alkoxy group, an aryloxy group, or an amino group is preferable, and a substituted amino group, specifically, an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is particularly preferable. The G ₁₀ is -SO ₂ -
In the case of a group, R ₁₀ is preferably an alkyl group, an aryl group or a substituted amino group.

In the general formula (N), G ₁₀ is preferably-
It is a CO- group or a -COCO- group, particularly preferably a -CO- group.

Next, specific examples of the compound represented by formula (N) are shown below. However, the present invention is not limited to the following compounds.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

[Table 6]

[0085]

[Table 7]

[0086]

[Table 8]

[0087]

[Table 9]

[0088]

[Table 10]

[0089]

[Table 11]

As the hydrazine derivative used in the present invention, in addition to the above, the following hydrazine derivatives are preferably used. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized.

(Formula 1) described in JP-B-6-77138
And 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, 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 the general 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 general formula (H) and general formula (Ha) described in JP-A-7-104426, specifically, compound H described on pages 8 to 15 of the same publication
-1 to H-44. As described in Japanese Patent Application No. 7-191007,
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. C), compounds represented by formulas (D), (E) and (F), specifically, compounds N-1 to N-30 described in the same publication. Japanese Patent Application 7-1
Compounds represented by the general formula (1) described in JP-A-91007, specifically, compounds D-1 to D-5 described in the same publication
5.

The hydrazine-based nucleating agent of the present invention may be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, It can be used by dissolving it in methylcellosolve 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 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 may be added to the silver halide emulsion layer or any other 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 nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 × per 1 mol of silver halide.
10 ⁻² mol is preferred, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferred, and 2 × 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferred.

Hereinafter, the processing agents such as the developing solution and the fixing solution and the processing method in the present invention will be described. However, needless to say, the present invention is not limited to the following description and specific examples.

In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.

The developer used in the present invention (hereinafter, both the development starting solution and the development replenisher are collectively referred to as a developer).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonic acid salts, and may be used alone or in combination. Further, from the viewpoint of developing ability, a combination of a dihydroxybenzene or an ascorbic acid derivative with a 1-phenyl-3-pyrazolidone or a combination of a dihydroxybenzene or an ascorbic acid derivative with a p-aminophenol is preferable. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred. Further, ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3
-Pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine and the like as p-aminophenol-based developing agents used in the present invention But N-methyl-p-
Aminophenols are preferred.

The dihydroxybenzene developing agent is usually 0.1
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / L to 0.6 mol / L, preferably 0.23 mol / L to 0.5 mol / L, It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is usually 0.1
It is preferably used in an amount of from 01 mol / l to 0.5 mol / l, more preferably from 0.05 mol / l to 0.3 mol / l. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is used in an amount of 0.01 mol / liter to 0.5 mol / liter, 1-phenyl-3-pyrazolidone or p-aminophenol. -Aminophenols
It is preferred to use from 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259, JP-A-60-93
The sugars described in 433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like, preferably carbonate , Boric acid is used. The amount of the buffer, particularly the carbonate, used is preferably at least 0.01 mol / l, particularly 0.05 to
1.5 mol / l.

The preservative used in the present invention includes sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. More than 0.2 mol / l of sulfite, especially 0.3 mol / l
It is used in an amount of 1 liter or more, but if it is added in an excessively large amount, it causes silver contamination in the developing solution. Therefore, the upper limit is preferably 1.2 mol / l. Particularly preferably, 0.35-0.
7 mol / l. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Other additives to be used 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, and heterocyclic mercapto compounds (eg, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole, and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventive agents. In addition to the compounds of the present invention, mercapto compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds can be used as antifoggants or black pepper.
It may be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2-thiol, chlorobenzotriazole, bromobenzotriazole, nitrobenzotriazole, methylbenzotriazole and the like. The amount of these additives is usually 0.01 to 1 liter of developer.
1010 mmol, more preferably 0.05-2 mmol.

Further, various organic and organic compounds are contained in the developing solution of the present invention.
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, 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 the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As the aminopolycarboxylic acid, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others JP-A-52-25632, 55-67747, 57-1
02624 and the compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in, for example, US Pat.
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid,
Amino trimethylene phosphonic acid and the like, and the other Research Disclosure 18170, JP-A-57-
Compounds described in 208554, 54-61125, 55-29883, 56-97347 and the like can be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, those described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, and JP-A-55-4
024, 55-4025, 55-126241, 55-65955, 55-6595
6 and the compounds described in Research Disclosure 18170 described above.

The organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of the developer.

Further, in addition to the compounds of the general formulas (2) to (4) as silver stain inhibitors in the developer, triazines having at least one mercapto group (for example, trimercaptotriazine, dimercaptotriazine, mercaptotriazine,
2-hydroxy-4,6-dimercaptotriazine, etc.),
Pyrimidines (eg, 2-mercaptopyrimidine, 2,6
-Dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine,
2,4,6-trimercaptopyrimidine and the like pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, -248587), the same pyrazine (eg, 2-mercaptopyrazine,
2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, and the like pyridazines (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimer Mercaptopyridazine, 3,
4,6-trimercaptopyridazine, etc.), the same triazole (eg, mercaptotriazole, dimercaptotriazole, 1-methyl-2,5-dimercaptotriazole, etc.), and the same thiadiazole (eg, 2-mercaptothiadiazole, 2,5-dimercapto) Thiadiazole, etc.), compounds described in JP-A-7-175177, US Pat.
The polyoxyalkyl phosphonate described in 1, etc. can be used. These silver stain inhibitors can be used alone or in combination of two or more.
It is preferably from 0.05 to 10 mmol, more preferably from 0.1 to 5 mmol, per liter. In addition, as a dissolution aid,
The compounds described in -267759 can be used. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The preferred pH of the developer is from 9.0 to 10.8, particularly preferably from 9.5 to 10.8. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As cations in the developer, potassium ions do not suppress the development as compared with sodium ions, and there is less jaggedness around the blackened portion called fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishment amount of the developing solution is per 1 m ² of the photosensitive material.
330 ml or less, preferably 325 to 50 ml. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration from the start solution.

As a fixing agent of the fixing processing agent in the present invention, ammonium thiosulfate, sodium thiosulfate, and sodium ammonium thiosulfate can be used. The amount of the fixing agent can be changed as appropriate, but is generally from about 0.7 to about
3.0 mol / l.

The fixing solution of the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, aluminum lactate, and aluminum gluconate. These are preferably contained at 0.01 to 0.15 mol / l as the aluminum ion concentration in the working solution. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

If desired, preservatives (eg, sulfites, bisulfites, metabisulfites, etc.) may be used in the fixing treatment agent in an amount of 0.015
Mol / l or more, preferably 0.02 mol / l ~
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / L to 1 mol / L, preferably 0.2 mol / L, of phosphoric acid, succinic acid, adipic acid and the like
0.7 mol / liter), compounds with aluminum stabilizing or water softening ability (eg gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid) 0.005 g of benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, sugars, boric acid, etc.
1 mol / l to 0.5 mol / l, preferably 0.00
5 mol / l to 0.3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include an anionic surfactant such as a sulfated sulfone oxide, a polyethylene-based surfactant, and an amphoteric surfactant described in JP-A-57-6840. Can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754 and 58-12253.
5, thiourea derivatives described in 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.No. 4,216,459, JP-A-64-4739, JP-A-1-4739, and 1-159
645 and the mercapto compound described in 3-101728, 4-1
70539, which may comprise a thiocyanate.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 7.0. The pH of the fixer is increased by mixing with a developer due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.7 or less for a non-hardened fixer.

The replenishment rate of the fixing solution is 5 per m ² of the photosensitive material.
00 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. By regenerating, the replenishment rate of the fixing solution can be reduced to 200 ml / m ² or less. As a reproduction device, for example, Fuji Hunt
Reclaim R-60 and others. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing agent in the present invention is a liquid agent, it is preferable to store it in a packaging material having low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water to 1 part of the concentrated liquid so as to have a predetermined concentration.

[0120] Although the developing agent and the fixing agent in the present invention can obtain the same results as the liquid agent even when they are solidified, the solid processing agent will be described below. The solid preparation in the present invention may be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid and vinyl compounds are preferred. In addition, JP-A-5-45805, column 48, line 48 to column 3
Line 13 can be helpful.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets or briquettes. It may be packaged in a similar layer configuration. These methods are described, for example, in JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g / cm.
³ are preferred, particularly tablets preferably 1.0 to 5.0 g / cm ^3, the granules is preferably 0.5 to 1.5 g / cm ^3.

As a method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-328
37, 4-78848, 5-93991, JP-A-4-85533, 4-8553
4, 4-85535, 5-134362, 5-97070, 5-04098,
5-224361, 6-138604, 6-138605, Japanese Patent Application 7-89123
Etc. can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material of the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, JP-A-6-242585-
6-242588, 6-247432, 6-247448, Japanese Patent Application 5-3066
4. A foldable shape as disclosed in JP-A-7-5664 and JP-A-7-5666 to 7-5669 is also preferable for reducing the storage space of the waste packaging material. These packaging materials
A screw cap, a pull top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and there is no particular limitation. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function,
A method of dissolving with a dissolving apparatus having a dissolving part and a part for storing a finished liquid as described in 7-235499, and replenishing from the stock part, JP-A-5-119454, JP-A-6-19102, JP-A-7-235499
-A method for supplying and dissolving a processing agent into the circulating system of an automatic developing machine as described in -261357, and dissolving by supplying a processing agent according to the processing of photosensitive material in an automatic developing machine with a built-in dissolving tank. However, any other known method can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferred from an environmental point of view. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method disclosed in JP-A-6-1910
2, the method described in 6-95331, and the like.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, washing including the stabilization processing is carried out. The liquid used for these is water or washing water. .) Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be smaller. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method for reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. The replenishing amount of washing is preferably 200 to 50 ml per 1 m ² of the photosensitive material. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-
Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. As a method for energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, 4-189
The method described in 80 or the like can be used.

In addition, a known water-soluble surfactant or antifoaming agent may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a washing system to prevent contamination by a dye eluted from the light-sensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Volume (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining, or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos. 2-201357 and 2-132435,
A bath containing a compound described in JP-A-1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath also contains an ammonium compound, a metal compound such as Bi or Al, a fluorescent whitening agent, various chelating agents, a membrane pH regulator,
Hardening agents, fungicides, sunscreens, alkanolamines and surfactants can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents can be solidified as in the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. In addition, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, US5439560
It is also possible to dispose after concentrating or liquefying or solidifying with a concentrating device such as described in US Pat.

In order to reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent evaporation of the liquid and oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises 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. Furthermore, during development and fixing and
A rinsing bath may be provided between the fixing water washing.

In the development processing of the present invention, the dry-to-dry 25 to 25
160 seconds is preferred, development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is preferably 25 to 50 ° C., and 3
0-40 ° C is preferred. Washing temperature and time is 0-50 ℃
It is preferably 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is about
The drying is performed at 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.
15534, the same 5-2256, heat roller drying as disclosed in the same 5-289294, there is drying by far infrared, etc.
A plurality of methods may be used in combination.

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-1-118832 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.

A polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. General formula (I) described in Japanese Patent Application No. 8-13592.
A polymer latex having an active methylene group represented by the formula:
6. A polymer latex having a core / shell structure described in Japanese Patent Application No. 8-13592, specifically, compounds P-1 to P-55. In addition, as the polymer latex used in the present invention, US Patent 2,763,65
2, 2,852,382, JP-A-64-538, JP-A-62-115152, JP-A-5
-66512, 5-80449, JP-B 60-15935, JP-B4-64058,
Polymer latexes composed of various monomers such as alkyl acrylates and alkyl methacrylates described in JP-A-5-45014, JP-B-45-5819, JP-B-46-22507, JP-A-50-73
625, Japanese Patent Application Nos. 5-300182 and 6-293681, and polymer latex copolymerized with a monomer having an active methylene group and a monomer such as an alkyl acrylate. An acid polymer described in JP-A-62-220947 can also be used. Particularly preferred is a polymer latex having a core / shell structure having a repeating unit composed of an ethylenically unsaturated monomer containing an active methylene group in a shell portion described in Japanese Patent Application No. 7-113256. Specifically, the compounds of K-1 to 23 described in Japanese Patent Application No. 7-113256 are preferably used.

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

Hardening agents described in JP-A-2-103536, page 18, upper right line, line 5 to line 17, upper right 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, page 7, line 7 of the publication. Specifically, the metal oxides described on page 2, lower right line 2 to the lower right line 10 of the same publication, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

The water-soluble dyes described in JP-A-2-103536, page 17, lower right, line 1 to upper right, line 18;

Solid disperse dyes represented by formula (FA), formula (FA1), formula (FA2) and formula (FA3) described in Japanese Patent Application No. 7-350753. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
Nos. (II-2) to (II-24) described in JP-A-7-1521
No. 12, (III-5) to (III-18), JP-A-7-15
(IV-2) to (IV-7) described in No. 2112.

Solid disperse dyes described in JP-A-2-294638 and US Pat. No. 5,342,743.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5; Specifically, compounds VI-1 to VI-15 described in the publication.

The following nucleation accelerators such as amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. JP-A-7-77783, page 48, line 2 to
Compounds described in line 37, specifically, compounds A-1) to A-73) described on pages 49 to 58. JP-A-7-843
(Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 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. General formula (1) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19 described
2-1 to 2-22, 3-1 to 3-3
6, compound 4-1 to 4-5, 5-1 to 5-4
1 compound, 6-1 to 6-58 compound and 7-1 to
Compounds 7-38.

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 1
The binder described in the second to 20th lines. The coating amount of binder such as gelatin, single side 5 g / m ² or less, preferably ^{1~4g / m 2, 15g / m} 2 or less on both sides, preferably 2 to 10 g / m ^2. The swelling ratio of the photosensitive material (percentage obtained by dividing the film thickness when immersed in water at 25 ° C. for 1 minute by the dry film thickness) is 75 to 150%, and the film surface pH is 5.0 to 6.5.

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

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EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of Emulsion A> 1 solution Water 1000 ml Gelatin 20 g Sodium chloride 2 g 1,3-Dimethylimidazolidin-2-thione 20 mg Sodium thiosulfonate 6 mg 2 solutions Water 600 ml Silver nitrate 150 g 3 solutions Water 600 ml Sodium chloride 54 g K ₃ IrCl ₆ 0.25 mg (NH ₄ ) ₂ RhC ₁₅ (H ₂₀ ) 0.06 mg Yellow blood salt 5 mg To one solution kept at 38 ° C., pH 4.5, while simultaneously stirring each of Solution 2 and Solution 3 for 20 minutes. In addition, 0.
Nuclear particles of 18 μm were formed. Subsequently, the following liquids 4 and 5 were added over 8 minutes to grow to 0.20 μm, and the particle formation was completed. Liquid 4 200 ml Silver nitrate 50 g Liquid 5 water 200 ml Sodium chloride 15 g Potassium bromide 7 g Potassium ferrocyanide 5 mg Thereafter, water was washed by flocculation according to a conventional method, and 45 g of gelatin was added. pH 5.6, pAg
Adjusted to 7.5, sodium thiosulfonate 10 mg, sodium thiosulfinate 3 mg, sodium thiosulfate 1
mg and triphenylphosphine selenide 1mg, chloroauric acid 5
mg, and chemically sensitized to obtain the highest sensitivity at 55 ° C., 0.15 g of potassium iodide was added, 200 mg of 1,3,3a, 7-tetraazaindene was added as a stabilizer, and as a preservative, Phenoxyethanol was added. Finally, an average silver chloride content of 95% (internal silver chloride content of 1%)
Thus, a silver iodochlorobromide cubic grain emulsion having an average grain size of 0.20 μm and containing 0.08 mol% of silver iodide was obtained. (Variation coefficient 9%)

Preparation of Emulsions B to D By changing the content of sodium chloride and potassium bromide in the two and / or five solutions of Emulsion A, the silver chloride contents of the inside of the grains and the surface layer of the grains were changed as shown in Table 9. A modified emulsion was prepared.

Preparation of Emulsions EG After grain formation as in emulsions A to D, 0.05
AgBr fine grains having a particle size of 1.mu.m are used per mole of silver halide.
Emulsions E to G having a silver bromide localized phase formed on the surface were prepared by adding 0 mol% equivalent.

Table 12 summarizes the constitutions of these emulsions.

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[Table 12]

Preparation of Coated Sample A sensitizing dye (1) (5.0 × 10 ⁻⁴ mol / mol Ag) was added to the obtained emulsion to perform 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 A
g, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound (3) (nucleation accelerator) 6.0 × 10 ⁻⁴ mol / mol. Ag was added. Next, the hydrazine derivatives shown in Tables 10 and 11 were used in an amount of 1.0 × 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 (4) 100 mg / m ² , and a dispersion of polyethyl acrylate 150 mg / m 2. ² , 150 mg / m ^{2 of} a latex copolymer (weight ratio 88: 5: 7) of methyl acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate,
Core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63), shell: styrene / 2
-Acetoacetoxyethyl methacrylate (weight ratio 84
/ 16), core / shell ratio = 50/50) to 150 mg /
m ² , 4 wt% of compound (5) based on gelatin was added, and the pH of the solution was adjusted to 5.5 using citric acid. They were coated on a subbed polyester support having a moisture-proof layer containing vinylidene chloride at a silver coating weight of 3.0 g / m ² and a gelatin coating weight of 1.3 g / m ² . On this, a protective layer upper layer and a protective layer lower layer of the following composition, and a UL layer of the following composition under this were applied.

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 Compound (6) (Gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (7) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (8) 20 mg / m ² Underlayer of protective layer Gelatin 0.5 g / m ² Compound (9) 15 mg / m ² 1,5-dihydroxy-2 - benzaldoxime 10 mg / m ² of polyethyl acrylate latex 150 mg / m ² UL layer gelatin 0.5 g / m ² of polyethyl acrylate latex 150 mg / m ² compound (5) 40mg / m ² compound (10) 10mg / 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 Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² compound (5) 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 0.25μ) 200 mg / m ²

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The obtained samples were evaluated for (1) photographic performance and (2) silver sludge and silver stain as shown below. Tables 13 and 14 show the results. As is clear from Tables 13 and 14, the sample of the present invention has a small sensitivity fluctuation due to running, is extremely hard, and reduces silver stain.

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[Table 13]

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[Table 14]

(1) Photographic performance evaluation A sample was passed through an interference filter having a peak at 633 nm.
Exposure was performed through a step wedge with xenon flash light having an emission time of 10 -6 sec. Using a developer (1) having the following composition, an AP-560 automatic developing machine manufactured by Fuji Photo Film Co., Ltd.
After developing at 5 ° C. for 30 seconds, fixing was performed with a fixing solution (1), followed by washing with water and drying. The sensitivity is 1.
Expressed as the reciprocal of the exposure amount giving 5;
The relative value of the sensitivity of each sample when it was set to 0 was calculated and set as S1.5. The higher the value, the higher the sensitivity. As an index (gamma) indicating the contrast of the image, a point between the point of Fog + density of 0.1 and the point of Fog + density of 3.0 on the characteristic curve was connected by a straight line, and the slope of this straight line was represented as a gamma value. That is, gamma = (3.0-0.1) / (log (density 3.
(Exposure amount giving 0) -log (exposure amount giving 0.1)], and a larger gamma value indicates harder photographic characteristics. As a graphic arts photosensitive material, gamma is preferably 10 or more, and more preferably 15 or more.

Further, an automatic developing machine manufactured by Fuji Photo Film Co., Ltd.
The AP-560 was subjected to a 100 m ² / day running process for 10 days for each of the photosensitive materials imagewise exposed at a blackening rate of 20%, and the sensitivity and gradation of the photosensitive materials after running were evaluated. . The variation in sensitivity is as follows: ΔS (sensitivity variation) = (S1.5 in running solution−S1.5 in Fr solution (fresh solution)) / (S1.
5) Expressed by × 100. Note that the developing temperature is 35 ° C and the fixing temperature is 34.
The processing was carried out at a temperature of ℃ and a development time of 30 seconds. The replenishment rate of the developer was 160 ml / m ² , the replenishment rate of the fixer was 160 ml / m ² , and the washing water was supplied at a flow rate of 5 liter / min.

(2) Silver Sludge and Silver Smear In the same manner as described above for the evaluation of photographic performance, 100 m ² of each image-wise exposed light-sensitive material at a blackening ratio of 20% using an automatic developing machine AP-560 manufactured by Fuji Photo Film Co., Ltd. / Day treatment for 10 days, visually observe the development of sludge in the developing tank, etc., and further treat FU-FILM's paper photosensitive material KU-150WP (6 cm × 30.3 cm) to obtain the degree of dirt. Was evaluated. Four or more silver sludge silver stains pose no practical problem.

The composition per liter of the concentrated solution of the developer (1) is shown below. 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 0.25 g 4-Hydroxymethyl-4-methyl-1-phenyl-3 -Pyrazolidone 1.35 g Compound of the general formula (1) The concentration in the working solution is described in Tables 13 and 14. Sodium erythorbate 9.0 g Diethylene glycol 60.0 g pH 10.7 When using, the ratio of 2 parts of water to 1 part of the above concentrated solution Dilute. The pH of the working solution is 10.5.

The composition of the solid developer (developer (2)) is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 63.0 g Sodium sulfite (raw powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g Less than or equal to briquette Diethylenetriamine / pentaacetic acid 42.0 g 5- Methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g Compound of the general formula (1) described in Tables 13 and 14 3- (5-mercaptotetrazol-1-yl) benzenesulfone Sodium acid salt 0.1 g Sodium erythorbate 6.0 g Potassium bromide 6.6 g Dissolve this in water to make 1 liter. pH 10.65

Here, in the form of raw materials, the raw powder was used as a general industrial product, and the alkali metal salt beads were commercially available. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treating agent was filled in a high-density polyethylene foldable container, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, a dissolution and replenishment device having an automatic opening mechanism disclosed in Japanese Patent Application Nos. 7-235499 and 7-235498 was used.

The prescription per liter of the concentrated solution of the fixing solution (1) is shown below. Ammonium thiosulfate 360 g Ethylenediamine tetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8.7 g Sodium gluconate 5.1 g Aluminum sulfate 25.2 g pH 4.85 For use, dilute 2 parts of water with 1 part of the above concentrate. The pH of the working solution is 4.8.

The composition of the solid fixing agent (fixing solution (2)) is shown below. Agent A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (raw powder) 19.0 g Sodium metabisulfite (raw powder) 18.0 g Anhydrous sodium acetate (raw powder) 42.0 g B agent (liquid) Ethylenediamine / tetraacetic acid・ 2Na dihydrate 0.03 g Citric anhydride 3.7 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make 50 ml. Agent A and Agent B were dissolved in water to make 1 liter. pH 4.8

As ammonium thiosulfate (compact), a flake product prepared by a spray-drying method was pressed and compressed by a roller compactor, and crushed into irregular shaped chips of about 4 to 6 mm, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the B agent container was sealed with a screw cap. Patent application Hei 7-23 for dissolution and replenishment
5499, a dissolution replenishing apparatus having an automatic opening mechanism disclosed in Japanese Patent Application No. 7-235498 was used.

Example 2 When the same experiment as in Example 1 was performed using a solid developer (developer (2)) and a solid fixing agent (fixer (2)), the same results as in Example 1 were obtained. Obtained.

Example 3 The same experiment as in Example 1 was performed using the following developer (3), and the same results as in Example 1 were obtained. The composition of the developer (3) is shown below. Diethylenetriamine-5 acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium bicarbonate 25 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.004 g 1-phenyl-5-mercaptotetrazole 02 g Sodium sulfite 2 g Compound of the general formula (1) Water described in Tables 13 and 14 is added to make 1 liter, and the pH is adjusted to 9.7. Example 4 In preparing the coating sample of Example 1, 2.0 × 10 ^-4 mol of the sensitizing dye (2) was used per 1 mol of silver instead of the sensitizing dye (1).
A sample was prepared in the same manner as in Example 1 except that 7.0 × 10 ^-4 mol of the sensitizing dye (3) was added.

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The sample thus obtained was evaluated in the same manner as in Example 1. However, the evaluation of photographic properties was 488 nm
The development was carried out in the same manner as in Example 1, except that the interference filter had a peak at As a result, the same result as in Example 1 was obtained.

Example 5 The sensitizing dye (2) and the sensitizing dye were prepared at the time of preparing the coating sample of Example 4.
Instead of (3), sensitizing dye (4) was added to 8.0 × per mole of silver.
A sample was prepared in the same manner as in Example 4 except that 10 ^-5 mol was added, the compound (14) was added at 2.3 × 10 ^-4 mol, and the compound (15) was added at 1.4 × 10 ^-4 mol. The sample thus obtained was evaluated in the same manner as in Example 4. However, the evaluation of photographic properties was performed by replacing the interference filter having a peak at 780 nm. As a result, the same result as in Example 1 was obtained.

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Example 6 The sensitizing dye (2) and the sensitizing dye were prepared at the time of preparing the coating sample of Example 4.
Instead of (3), sensitizing dye (5) per 7.0 mol of silver was used.
A sample was prepared in the same manner as in Example 4 except that 10 ^-4 mol was added. The sample thus obtained was evaluated in the same manner as in Example 4. However, the evaluation of photographic properties was 3200 ° K
Exposed to tungsten light. As a result, the same result as in Example 1 was obtained.

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Claims (1)

[Claims] 1. The method according to claim 1, wherein the silver chloride content on the support is 70 mol%.
The above silver halide grains, wherein at least one layer comprising a surface layer having a lower silver chloride content than the inside and / or a silver halide grain having a localized phase having a lower silver chloride content than the inside on the surface. A method for processing a silver halide photographic material, comprising developing a silver halide photographic material having a silver halide emulsion layer in the presence of at least one compound represented by formula (I). General formula (I) In the general formula (I), D and E are -CH = group, -C (R
₀ ) = represents a group or a nitrogen atom, wherein R ₀ represents a substituent. L _1, L _2, L ₃ represents a hydrogen atom, a halogen atom or a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, an optionally substituted group bonded to phosphorus ring any atom, L ₁
~L ₃ may be the same or different. Where L ₁ ,
At least one of L ₂ , L ₃ and R ₀ is a —SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group)
Represents When E and D represent one nitrogen atom and one carbon atom, E is a nitrogen atom and D is a carbon atom (-CH =
Or -C (R ₀ ) = group), wherein L ₂ and L ₃ do not represent a hydroxy group.