JPH09211803A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce contamination with silver and to improve the photographic property by treating a photosensitive material including an emulsion layer containing specified silver halide particles and a hydrophilic colloid layer and contains a hydrazine deriv. and an accelerating agent for formation of nuclei with a developer containing a specified compd. SOLUTION: This photographic photosensitive material has a silver halide emulsion layer containing such silver halide particles that have <=0.25μm average particle size and has >=90mol% silver chloride containing 1×10<-8> to 1×10<-4> mol of the V to VIII group transition metals per one mol of silver. This emulsion layer and other hydrophilic colloid layers contain a hydrazine deriv. and an accelerating agent for formation of nuclei. The photosensitive material is treated with a developer containing a compd. expressed by a formula. In the formula, Z<1> represents the group of nonmetal atoms necessary to form a five or six- member nitrogen-contg. heteroring formed by the combination of N and C and Z<1> contains R<1> and (SX<2> )n as substituents. R<1> is a substituent bonded to the ring with a hydrogen atom or carbon atom, X<1> and X<2> are hydrogen atoms or cations, and (n) is 0, 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and particularly to a method for processing a silver halide photographic light-sensitive material capable of obtaining a high contrast negative image useful in a photomechanical process. It is about the method.

[0002]

2. Description of the Related Art Generally, in developing a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material or a light-sensitive material),
From the viewpoint of quickness, simplicity, and handleability, an automatic processor is used. In recent years, electronic plate making using a computer has become widespread and the process has been simplified. Therefore, development processing is required to be quick and simple in accordance with the process. In order to meet these requirements, there is a method of improving the light-sensitive material such as reducing the film thickness of the light-sensitive material and changing the halogen composition to silver chloride, and at the same time, increasing the activity of the developer is also one means. is there. In the processing of the black-and-white sensitive material, the activity can be increased by increasing the concentration of the developing agent, but the deterioration due to air oxidation is remarkable.

By the way, although it has been known for a long time to use a sulfite salt for preventing deterioration of a developing solution, since it has a dissolving action of silver halide, silver is eluted from the photosensitive material as a silver sulfite complex in the developing solution. Resulting in. This silver complex is reduced in the developer and gradually adheres to and accumulates on the developing tank or roller. This is called silver stain or silver sludge, which adheres to the photosensitive material to be processed and stains the image or pollutes the automatic developing machine itself, so that periodic cleaning and maintenance are required.

As a method of reducing these silver stains, DL-6,8-dithiooctanoic acid described in US Pat. No. 3,318,701 and British Patent No. 1144481 o
It is known to add mercaptobenzoic acid, the aliphatic mercaptocarboxylic acids described in US Pat. No. 3,628,955, etc. to the developer. However, these compounds have the effect of suppressing the development itself, accompanied by a decrease in sensitivity and Dmax, it can not be used in large amounts,
If the amount is small, the effect of suppressing silver elution is insufficient, and therefore a sufficient effect of preventing silver stain cannot be obtained.

Further, it has been found that these compounds cause adverse effects such as impairing the effect of the hydrazine derivative added for obtaining good photographic characteristics, and causing poor defects in fixing due to long-term running processing. .

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method which reduces silver stains generated when processing a silver halide photographic light-sensitive material capable of rapid processing and has good photographic properties. Especially.

[0007]

The above object has been achieved by the following constitution. That is, at least one silver halide emulsion layer is provided on a support, and the silver halide emulsion contains from 1 × 10 ⁻⁸ mol to 1 × 10 mol of at least one transition metal of Group V to VIII per mol of silver. ^-4 mol, containing silver chloride grains having a silver chloride content of 90 mol% or more and an average grain size of 0.25 μm or less, and at least one layer of the emulsion layer and other hydrophilic colloid layers is nucleated with a hydrazine derivative. An image forming method characterized in that a silver halide photographic light-sensitive material containing an accelerator is treated with a developer containing a compound represented by the general formula (1). General formula (1)

[0008]

Embedded image

In the formula, Z ¹ represents a non-metal atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle in cooperation with N and C, and Z ¹ represents R ¹ and ( SX ² )
_{have n} . Here, R ¹ is a hydrogen atom, a halogen atom,
Alternatively, it represents a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. X ¹ and X ² are hydrogen atoms or cations, and n is 0, 1 or 2. Further, two kinds of radicals obtained by removing one arbitrary hydrogen atom from Z ¹ may combine to form a bis type structure.

Next, the general formula (1) will be described in detail. Z ¹
Represents a non-metal atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle in cooperation with N and C.
The 5-membered nitrogen-containing aromatic heterocycle formed of Z ¹ , N and C is a combination of elements selected from carbon, oxygen and sulfur in addition to nitrogen, and is further a hydrocarbon ring or heterocycle. May be condensed with, for example, pyrazole, imidazole, oxazole, thiazole, triazole, thiadiazole, oxadiazole, indazole, benzimidazole, benzoxazole,
Examples thereof include benzothiazole, pyrazolotriazole and pyrrolotriazole. The 5-membered nitrogen-containing aromatic heterocycle is preferably triazole, thiadiazole, oxadiazole, benzimidazole, benzoxazole, benzothiazole, pyrazolotriazole or pyrrolotriazole, more preferably triazole,
Thiadiazole, oxadiazole and benzimidazole, most preferably triazole. Z ¹ ,
The 6-membered nitrogen-containing aromatic heterocycle formed by N and C is a monocyclic ring or a ring condensed with a carbon ring or a heterocycle, such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, phthalazine, It is quinoxaline, quinazoline, shinoline, phenanthridine, phenanthroline, naphthyridine, pteridine, purine, triazolopyrimidine, imidazolopyridine, triazolopyridine, imidazolotriazine, triazolotriazine. The 6-membered nitrogen-containing aromatic heterocycle is preferably pyrazine, pyrimidine, pyridazine, triazine, phthalazine, quinoxaline, quinazoline, naphthyridine, pteridine, purine, triazolopyrimidine, imidazolopyridine, triazolopyridine,
Imidazolotriazine, triazolotriazine,
Pyrimidine, pyridazine, triazine, pteridine, purine, triazolopyrimidine, imidazolotriazine and triazolotriazine are more preferable, and pyrimidine, triazine and purine are most preferable.

R ¹ represents a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. As the group bonded by the carbon atom of R ¹ , an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carboxyl group,
A cyano group and a heterocyclic group, which are bonded by an oxygen atom, are a hydroxy group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, acyloxy group, carbamoyloxy group, and sulfonyloxy group are bonded to each other by a nitrogen atom, such as acylamino group, amino group, alkylamino group, arylamino group, heterocyclic amino group, ureido group, and sulfamoyl group. The amino group, the alkoxycarbonylamino group, the aryloxycarbonylamino group, the sulfonamide group, the imide group, and the heterocyclic group, which are bound by a sulfur atom, include an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, and an alkoxysulfonyl group. Group, an aryloxysulfonyl group, a sulfonyl group, a sulfo group, and a sulfinyl group. These may be further substituted with the groups mentioned as R ¹ . R ¹ may be plural, and if possible, two R ¹ may combine to form a ring.

The R ¹ will be described in more detail. The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and examples thereof include methyl, ethyl, isopropyl, t-butyl, benzyl and cyclopentyl. The alkenyl group has 2 to 10 carbon atoms, for example vinyl, 1-
Examples include propenyl, 1-hexenyl and styryl.
The alkynyl group has 2 to 10 carbon atoms and includes, for example, ethynyl, 1-butynyl and phenylethynyl. The aryl group is an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 8 carbon atoms, and includes, for example, carbamoyl, N-ethylcarbamoyl,
It is N-phenylcarbamoyl. The alkoxycarbonyl group has 2 to 8 carbon atoms, such as methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 12 carbon atoms,
For example, phenoxycarbonyl. The acyl group has 1 to 8 carbon atoms, such as acetyl and benzoyl. The heterocyclic group linked by a carbon atom on the ring is a 5- or 6-membered saturated or unsaturated heterocycle having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, The number of hetero atoms constituting the ring and the number of elements may be one or plural, and examples thereof include 2-furyl, 2-thienyl, 2-pyridyl, and 2-imidazolyl.

The alkoxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and is, for example, methoxy or 2-
Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 12 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m-.
(3-hydroxypropionamide) phenoxy. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or more, and examples thereof include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy,
2-pyridyloxy. The acyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy, and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has a carbon number of 1 to 8, and examples thereof include methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 10 carbon atoms,
It preferably has 1 to 6 carbon atoms, such as acetylamino and benzoylamino. The alkylamino group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylamino, N- (2-hydroxyethyl) amino and N- (3-dimethylaminopropyl).
It is Amino. Arylamino group has 6 to 1 carbon atoms
Those of 0 are, for example, anilino and N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or plural, and examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino, and 4-pyridylamino. The ureido group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
10 to 10, preferably 0 to 5 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and is, for example, methoxycarbonylamino. The aryloxycarbonylamino group has 7 to 12 carbon atoms, such as phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The sulfonamide group has 1 to 10 carbon atoms, preferably 1 carbon atom.
To 6, for example, methanesulfonamide and p-toluenesulfonamide. The imide group has 4 carbon atoms
And N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocyclic ring composed of a nitrogen atom and at least one of a carbon atom, an oxygen atom or a sulfur atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 10 carbon atoms,
Preferably, it has 1 to 5 carbon atoms, such as methylthio,
It is 2-carboxyethylthio. The arylthio group has 6 to 12 carbon atoms, for example, phenylthio, 2
-Carboxyphenylthio. The heterocyclic thio group is a 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and which constitutes a ring. The number of atoms and the number of elements may be one or plural, and examples thereof include 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms
It has 0, preferably 0 to 6 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl. The alkoxysulfonyl group has 1 to 1 carbon atoms
It preferably has 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxysulfonyl. The aryloxysulfonyl group has 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.

R ¹ is preferably hydrogen atom, alkyl group, aryl group, carbamoyl group, acyl group, cyano group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, sulfone. Amido group, alkylthio group, arylthio group, sulfamoyl group, sulfonyl group, more preferably hydrogen atom, alkyl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, alkylthio group, most preferably A hydrogen atom, an alkyl group, an alkoxy group, an amino group, and an alkylthio group.

X ¹ and X ² are hydrogen atoms or cations. Examples of the cation include sodium, potassium, lithium, calcium, ammonium, tetrabutylammonium and triethylammonium. X
¹ and X ² are preferably a hydrogen atom, sodium,
Potassium and ammonium. n is preferably 1 or 2.

From the general formula (1), a radical having two arbitrary hydrogen atoms bonded to each other to form a bis type structure is preferably represented by the following general formula (2). General formula (2)

[0022]

Embedded image

In the formula, Z ²¹ and Z ²² each represent a group obtained by removing one hydrogen atom from Z ^{1 in the} formula (1), and X ²¹ and X ²² have the same meaning as X ¹ . L ² is a divalent linking group (alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group and -O-, -S-, -NH-, -CO.
-, --SO _2-, etc., which are linked by a group consisting of a single or a combination thereof. These preferred ones are also the same as in the formula (1).

Examples of the alkylene group for L ² include ethylene, trimethylene, pentamethylene, propylene and 2
-Butene-1,4-yl, 2-butene-1,4-yl,
p-xylylene. The alkenylene group is, for example, ethene-1,2-yl. The alkynylene group is ethyn-1,2-yl. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ² represents an alkylene group, a —NH (alkylene) NH— group, —O
(Alkylene) O-group, -S (alkylene) S-group,-
NH (alkylene) CONH (alkylene) NH- group,
-NH (alkylene) O (alkylene) NH- is preferable, and -NH (alkylene) NH- group and -O (alkylene) O- group are more preferable.

Of the compounds of the present invention represented by the general formula (1), those represented by the following general formulas (3) to (10) are preferable. General formula (3)

[0026]

Embedded image

In the formula, R ³¹ and X ³¹ have the same meanings as R ¹ and X ^{1 in} formula (1), respectively. R ³¹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an optionally substituted amino group, a mercapto group or an alkylthio group, more preferably a hydrogen atom, an alkyl group, a hydroxy group, An optionally substituted amino group and a mercapto group are preferred, and a hydrogen atom, an alkyl group and a mercapto group are most preferred. R ³² is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group or an optionally substituted amino group. R ³² is preferably a hydrogen atom, an alkyl group, a hydroxy group,
It is an optionally substituted amino group, more preferably a hydrogen atom or an alkyl group. General formula (4)

[0028]

Embedded image

In the formula, R ⁴¹ , R ⁴² and X ⁴¹ have the same meanings as R ³¹ , R ³² and X ^{31 in the} general formula (3), respectively, and the preferred ranges are also the same. General formula (5)

[0030]

[Chemical 6]

In the formula, R ⁵¹ and X ⁵¹ have the same meanings as R ³¹ and X ^{31 in} formula (3), respectively. R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an optionally substituted amino group, a mercapto group or an alkylthio group, more preferably an alkyl group or an optionally substituted group. An amino group, a mercapto group and an alkylthio group are preferred, and a mercapto group and an alkylthio group are most preferred. General formula (6)

[0032]

Embedded image

In the formula, R ⁶¹ , R ⁶² and X ⁶¹ have the same meanings as R ³¹ , R ³² and X ^{31 in} formula (3), respectively. R ⁶¹
Preferably a hydrogen atom, an alkyl group, an aryl group,
A heterocyclic group, a hydroxy group, an alkoxy group, an optionally substituted amino group, a mercapto group, an alkylthio group, more preferably a hydroxy group, an alkoxy group,
An amino group which may be substituted, a mercapto group and an alkylthio group are preferred, and a hydroxy group, an amino group which may be substituted and a mercapto group are most preferred. R ⁶² is preferably a mercapto group. General formula (7)

[0034]

Embedded image

In the formula, R ⁷¹ , R ⁷² and R ⁷³ have the same meanings as R ⁶¹ , R ⁶² and R ^{62 in the} general formula (6), respectively, and the preferred ranges are also the same. However, at least one of them is a mercapto group. More preferably, R ⁷³ is a mercapto group. General formula (8)

[0036]

Embedded image

In the formula, R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ have the same meanings as R ⁶¹ , R ⁶² , R ⁶¹ and R ^{62 in the} general formula (6), respectively, and the preferred ranges are also the same. However, at least one of them is a mercapto group. R ⁸³ is most preferably an optionally substituted amino group or a hydrogen atom. More preferably, R ⁸⁴ is a mercapto group. General formula (9)

[0038]

Embedded image

In the formula, R ⁹¹ , R ⁹² and R ⁹³ have the same meanings as R ⁶¹ , R ⁶² and R ^{61 in the} general formula (6), respectively, and their preferable ranges are also the same. However, at least one of them is a mercapto group. More preferably, R ⁹² or R ⁹³ is a mercapto group.

[0040]

Embedded image

In the formula, R ¹⁰¹ to R ¹⁰⁴ and X ¹⁰¹ have the same meanings as R ¹ and X ^{1 in} formula (1), respectively.
R ¹⁰¹ to R ¹⁰⁴ are preferably a hydrogen atom, a sulfo group, a carboxyl group, a hydroxy group or a sulfamoyl group, more preferably a hydrogen atom or a sulfo group, and R
Most preferably, ¹⁰³ is a sulfo group.

Of the general formulas (3) to (10), the general formulas (3), (5) to (9) are more preferable, and the general formulas (3), (6) and (8) are most preferable. Next, specific examples of the compound represented by the general formula (1) in the present invention will be shown, but the compound is not limited thereto.

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

[Chemical 21]

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

The compound represented by the general formula (1) of the present invention is described in the following patents and the patents / documents cited therein. That is, JP-A-4-301837,
5-61159, 6-230525 and JP-A-58-58.
169147, 62-56959, U.S. Pat.
892, JP-A-3-53244, and JP-A-3-282457,
5-61159, 5-303179, 4-362
942, JP-B-46-11630, JP-A-6-1753
02, 6-258787 and the like.

When the compound represented by the general formula (1) of the present invention is added to the developing solution, the amount of the compound is 0.1% per liter of the developing solution.
A range of 01 to 10 mmol is preferred, 0.1 to 5
The millimolar range is particularly preferred.

The method of adding the compound represented by the general formula (1) of the present invention to a silver halide photographic material is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol). ), Ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also, by well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It can also be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare and use an emulsified dispersion. Alternatively, the powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

Next, the hydrazine derivative used in the present invention will be described. The hydrazine derivative used in the present invention is represented by the general formula (H). General formula (H)

[0062]

Embedded image

In the formula, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or Represents a hydrazino group, G1 is --C
O- group, -SO ₂ - group, -SO- group,

[0064]

Embedded image

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In formula (H), the aliphatic group represented by R ₁ is preferably a substituted or unsubstituted, straight-chain, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms. . In the general formula (H), R
_The aromatic group represented by ₁ is a monocyclic or bicyclic aryl group, for example, a benzene ring or a naphthalene ring. The heterocyclic group represented by R ₁ is a monocyclic or bicyclic aromatic or non-aromatic heterocycle, which may be condensed with an aryl group to form a heteroaryl group. , For example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring,
Quinoline ring, isoquinoline ring, benzimidazole ring,
Examples thereof include a thiazole ring and a benzothiazole ring. R
Preferred as ₁ is an aryl group. R ₁ may be substituted, and typical examples of the substituent include an alkyl group (including an active methine group), an alkenyl group, an alkynyl group, an aryl group, a group including a heterocycle, and a quaternized nitrogen atom. A group containing a heterocycle containing (for example, a pyridinio group), a hydroxy group, an alkoxy group (including a group containing a repeating ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group A group containing a hydrazino group, a group containing a quaternary ammonio group, a (alkyl, aryl, or heterocycle) thio group, a (alkyl or aryl) sulfonyl group, a (alkyl or aryl) sulfinyl group, a sulfo group, a sulfamoyl group, Acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, nitro group, phosphoric acid amide group, group containing phosphoric ester structure, acylurea Group with granulation, a group containing a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure. Preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably having 1 to 20 carbon atoms), and alkoxy groups (preferably having 1 to 20 carbon atoms). 20), substituted amino group (preferably having 1 to 20 carbon atoms), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms) ), A ureido group (preferably having 1 to 30 carbon atoms), a carbamoyl group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) and the like. .

In the general formula (H), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, a benzene ring. Is included. As the heterocyclic group, at least one nitrogen, oxygen,
And a 5- to 6-membered ring compound containing a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group, a quinolinio group,
There is a quinolinyl group. Pyridyl or pyridinio groups are particularly preferred. Alkoxy group has 1 to 8 carbon atoms
And the aryloxy group is preferably a monocyclic one, and the amino group is preferably an unsubstituted amino group, or an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a heterocyclic amino group. . R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Among the groups represented by R ₂ , when G ₁ is a —CO— group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl) is preferable. Group, pyridiniomethyl group, 3-
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methane) Sulfonamidophenyl group, o-carbamoylphenyl group, 4-cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom or an alkyl group. When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group). Alternatively, a substituted amino group (eg, a dimethylamino group, etc.) and the like are preferable. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferable, and a substituted amino group (for example, 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group, Anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group, etc.) are preferred. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms For example, Japanese Patent Laid-Open No. 63-297
No. 51 and the like.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (H) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (H) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler 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 group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (H) may have an adsorptive group adsorbing to silver halide incorporated therein. Examples of the adsorptive group include an alkylthio group, an arylthio group, a thiourea group, a thioamide group,
U.S. Pat. Nos. 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045 and JP-A-59-201045, such as mercapto heterocyclic groups and triazole groups. 201046, 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 ₁ or R ₂ in the general formula (H) may contain a plurality of hydrazino groups as a substituent. At this time, the compound represented by the general formula (H) is a multimer with respect to the hydrazino group. And specifically, for example, JP-A-64-86134.
And compounds described in JP-A Nos. 4-16938 and 5-97091.

In the present invention, a particularly preferred hydrazine derivative will be described. R ₁ is particularly preferably a substituted phenyl group, a ballast group through a sulfonamide group, an acylamino group, a ureido group, or a carbamoyl group, an adsorption group to silver halide, a group containing a quaternary ammonio group,
A group containing a repeating unit of an ethyleneoxy group, alkyl,
It may be substituted with an aryl or heterocyclic thio group, a group capable of dissociating in an alkaline developing solution (carboxyl group, sulfo group, acylsulfamoyl group, etc.), or a hydrazino group capable of forming a multimer. preferable. R ₁ is most preferably a phenyl group substituted with a benzenesulfonamide group, and the substituent of the benzenesulfonamide group preferably has any of the groups described above. G ₁ is preferably a —CO— group or a —COCO— group, particularly preferably a —CO— group. When G ₁ is a —CO— group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or an o-hydroxymethyl group), and G ₁ is —COCO. When it is a -group, a substituted amino group is particularly preferable.

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

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

[Table 5]

[0080]

[Table 6]

[0081]

[Table 7]

[0082]

[Table 8]

As the hydrazine derivative used in the present invention, the following hydrazine derivative is preferably used in addition to the above. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized. A compound represented by (Chemical Formula 1) described in JP-B-6-77138.
Compounds described on pages 4 and 4. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP-A-6
Compounds represented by formulas (4), (5) and (6) described in JP-A-230497, specifically, compounds 4-1 to 4 described on pages 25 and 26 of the same publication. -1
0, compounds 5-1 to 5-42 on pages 28 to 36,
And compounds 6-1 to 6 described on pages 39 and 40.
-7. General formula (1) described in JP-A-6-289520
And compounds represented by formula (2), specifically, compounds 1-1) to 1-17) and 2-1) described on pages 5 to 7 of the same publication. 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. JP-A-6-3139
A compound represented by Chemical Formula 1 described in No. 51, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-561
Compounds represented by general formula (I) described in No. 0, specifically, Compounds 1-1 to 1-3 described on pages 5 to 10 of the same publication
8. 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 publication. JP-A-7-10442
Compounds represented by General Formula (H) and General Formula (Ha) described in No. 6, specifically Compounds H-1 to H-44 described on pages 8 to 15 of the same publication. A compound described in Japanese Patent Application No. 7-191007 characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, and particularly a compound represented by the general formula (A) ), General formula (B), general formula (C), general formula (D),
Compounds represented by formula (E) and formula (F), specifically compounds N-1 to N-30 described in the same publication. Japanese Patent Application 7
-191007, compounds represented by formula (1), specifically, compounds D-1 to D-5 described in the publication.
5.

The hydrazine-based nucleating agent of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, It can be used by dissolving it in methyl cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced 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 any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. 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 × with ^respect to 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.

The nucleation accelerator used in the present invention includes
Examples thereof include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described in pages 49 to 58. JP-A-7-84
No. 331, (Chem. 21), (Chem. 22) and (Chem. 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. 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.

The nucleation accelerator preferably used in the present invention is an onium salt compound represented by the general formulas (A-1), (A-2), (A-3) and (A-4). This will be described in detail below.

First, the general formula (A-1) will be described in detail.

[0089]

Embedded image

Where R₁, R_Two, R_ThreeIs an alkyl group,
Low alkyl group, aralkyl group, aryl group, alkenyl
Group, cycloalkenyl group, alkynyl group, heterocyclic residue
And may further have a substituent.
m represents an integer, L is bound to the P atom and its carbon atom
Represents an m-valent organic group, and n represents an integer of 1 to 3.
X represents an n-valent anion, and X is linked to L.
You may. R₁, R_Two, R_ThreeExamples of groups represented by
Is methyl, ethyl, propyl, isopropyl
Group, butyl group, isobutyl group, sec-butyl group, tert
-Butyl group, octyl group, 2-ethylhexyl group, dode
Linear or straight chain such as syl, hexadecyl, octadecyl, etc.
Is a branched alkyl group, substituted or unsubstituted benzyl group, etc.
Aralkyl group; cyclopropyl group, cyclopentyl
Group, cycloalkyl group such as cyclohexyl group, phenyl group
Aryl such as ruthel group, naphthyl group and phenanthryl group
Groups; groups such as allyl group, vinyl group, 5-hexenyl group, etc.
Lucenyl group; cyclopentenyl group, cyclohexenyl group
Such as cycloalkenyl groups; such as phenylethynyl groups
Alkynyl group; pyridyl group, quinolyl group, furyl group, a
Midazolyl group, Thiazolyl group, Thiadiazolyl group, Ben
Zotriazolyl group, benzothiazolyl group, morpholyl
Group, pyrimidyl group, pyrrolidyl group, etc.
No. Examples of substituents substituted on these groups
Is R₁, R_Two, R_ThreeIn addition to the groups represented by
Halogen source such as child, chlorine atom, bromine atom, iodine atom
Child, nitro group, 1,2,3 amino group, alkyl or
Reel ether group, alkyl or aryl thioether
Group, carbonamido group, carbamoyl group, sulfone amine
Group, sulfamoyl group, hydroxyl group, sulfoxy group
Group, sulfonyl group, carboxyl group, sulfonic acid group,
Ano group or oxycarbonyl group, acyl group
You. As an example of the group represented by L, m and n are 1
When you forgot, R₁, R_Two, R_ThreeAnd a group synonymous with
When m and n each represent an integer other than 1,
Trimethylene group, tetramethylene group, hexamethylene group
Group, pentamethylene group, octamethylene group, dodecamet
Polymethylene group such as len group, phenylene group, biphenyl
Divalent aromatic groups such as len group and naphthylene group, trimethylene
Polyvalent aliphatic groups such as methyl group and tetramethylene methyl group
Group, phenylene-1,3,5-toluyl group, phenylene
No polyvalent aromatic group such as -1,2,4,5-tetrayl group
And so on. As an example of an anion represented by X
Is a halo such as chloride, bromide, or iodide.
Gen ion, acetate ion, oxalate ion,
Carboxy such as fumarate ion and benzoate ion
Sylate ion, p-toluene sulfonate, methan
Ruphonate, butane sulfonate, benzene sulfonate
Sulfonate ion, sulfate ion, perchlorate ion, etc.
ON, carbonate ion, and nitrate ion. General formula
In (A-1), R₁, R_Two, R_ThreeIs preferably carbon number
A group having 20 or less, particularly an aryl group having 15 or less carbon atoms
Preferred. m is preferably 1 or 2, and m represents 1.
At this time, L is preferably a group having 20 or less carbon atoms, and total carbon
Alkyl group, aralkyl group or aryl having a prime number of 15 or less
Ru groups are particularly preferred. When m represents 2, it is represented by L
The divalent organic group is preferably an alkylene group or arylene.
A group or a divalent group formed by combining these groups,
In addition, these groups and -CO- group, -O- group, -NR_Four−
Group (however R_FourIs a hydrogen atom or R₁, R_Two, R_ThreeSame as
And a plurality of R's in the molecule._FourWhen there is
They can be the same or different, and even
May be bonded to any group), -S- group, -SO- group,-
SO_TwoA divalent group formed by combining groups.
When m represents 2, L is bonded to the P atom at its carbon atom
Particularly preferred is a divalent group having a total carbon number of 20 or less.
Yes. When m represents an integer of 2 or more, R₁,
R_Two, R_ThreeExists in plurals, respectively,
R₁, R_Two, R_ThreeAre the same but different
May be. n is preferably 1 or 2, m is 1 or 2
Is preferred. X is R₁, R_Two, R _ThreeOr L
To form an inner salt. In the general formula (A-1) of the present invention,
Many of the compounds represented are known and used as reagents.
Are commercially available. As a general synthetic method, phosphine
Acids such as alkyl halides and sulfonates
How to react with any alkylating agent: or phosphoni
There is a method of exchanging the counter anion of um salts by a conventional method.
You. Specific examples of the compound represented by the general formula (A-1) are shown below.
Show. However, the present invention is not limited to the following compounds
There is no.

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

General formula (A-2) and general formula (A-3) will be described in more detail.

[0096]

Embedded image

In the formula, A represents an organic group for completing a heterocycle (including those having a substituent), and may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and further benzene. The ring may be condensed. As a preferred example, A can be a 5- or 6-membered nitrogen-containing heterocycle, and a more preferred example is a pyridine ring. B, 2 divalent group represented by C is an alkylene, arylene, alkenylene, -SO ₂ -, - SO
-, -O-, _-S- , -N ( _RN )-, -C (= O)
It is preferable that-, -P (= O)-are used alone or in combination. However, R _N represents an alkyl group, an aryl group, or a hydrogen atom. Particularly preferable examples are B and C.
Can include alkylene, arylene, -O-, and -S- alone or in combination.
R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms,
Each may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), a substitution or Unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p
-Bromobenzoyl group, acetyl group, etc.), (alkyl or aryl) oxycarbonyl group, sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group , Carbamoyl group, ureido group,
Examples include unsubstituted or alkyl-substituted amino groups, cyano groups, nitro groups, alkylthio groups, and arylthio groups.
As a particularly preferred example, R ₁ and R ₂ each have 1 to 1 carbon atoms.
Represents an alkyl group of 0. Examples of preferred substituents include
Examples thereof include a carbamoyl group, an oxycarbonyl group, an acyl group, an aryl group, a sulfo group, a carboxy group and a hydroxy group. R ₃ and R ₄ represent a hydrogen atom or a substituent, and there may be a plurality of them, and they may be the same or different. Examples of the substituent include R ₁ and R described above.
_It is selected from the substituents listed as substituents for the alkyl group of ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. A
Examples of the substituent on the heterocycle include a group having the same meaning as R ₃ and R ₄ . X represents an anionic group, but X is not necessary in the case of an inner salt. Examples of X include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 16
3 (1962). )

Specific compounds represented by formulas (A-2) and (A-3) are shown below, but the invention is not limited thereto.

[0099]

Embedded image

[0100]

Embedded image

General formula (A-4) will be described in more detail.

[0102]

Embedded image

The nitrogen-containing heterocycle containing Z may contain a carbon atom, a hydrogen atom, an oxygen atom or a sulfur atom in addition to the nitrogen atom, and the benzene ring may be condensed. It also includes those having a substituent. The heterocycle formed is preferably a 5- or 6-membered ring, more preferably a pyridine ring, a quinoline ring, or an isoquinoline ring. R is preferably an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and may be a straight-chain, branched or cyclic alkyl group. An alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is most preferable.
X ⁻ represents an anion group, but in the case of an intramolecular salt, X ⁻ is not necessary. Examples of X ⁻ include chlorine ion, bromine ion,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

The groups represented by Z and R may be substituted and preferred substituents include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group). Group, p-chlorophenyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, Ethoxy group),
Aryloxy group, oxycarbonyl group, amide group, sulfamoyl group, carbamoyl group, sulfonamide group,
It represents a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group and an arylthio group. Examples of particularly preferable substituents include an oxycarbonyl group, a carbamoyl group, an acyl group, an aryl group, a sulfo group, a carboxy group and a hydroxy group. Further, as the substituent of the nitrogen-containing heterocycle containing Z, other substituted or unsubstituted alkyl group (for example, methyl group,
And a substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.) are also preferable. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (Reference, Quart. Rev., 16, 163 (1962).) Specific compounds of the general formula (A-4) are shown below, but the present invention is not limited thereto.

[0105]

Embedded image

[0106]

Embedded image

Amino compounds are also preferably used as the nucleation accelerator, and the following compounds are particularly preferably used.

[Chemical Formula 2] described in JP-A-7-84331
1) Compounds represented by (Chemical Formula 22) and (Chemical Formula 23), specifically, compounds described on pages 6 to 8 of the same publication. Compounds represented by the general formula [Na] described in JP-A-7-104426, specifically, compounds Na-1 to Na-22 described on pages 16 to 20 of the same. Japanese Patent Application No. 7-37817
Compounds represented by general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) and general formula (7) described in Specifically, the compounds of 1-1 to 1-19 described in the same specification, 2-1 to 2-
22 compounds, 3-1 to 3-36 compounds, 4-1 to 4
-5 compound, 5-1 to 5-41 compound, 6-1 to 6
Compounds of -58 and 7-1 to 7-38.

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

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

Next, the V to VIII group transition metals used in the present invention will be described. Preferred in the present invention (e) ~ (h)
Group transition metals include Rh, Ru, Re, Os, and I.
r, Cr and the like. 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 as a ligand, a halogen, an amine,
Those having oxalate etc., such as hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium (III) complex salt, trizalatrodium (I)
II) Complex salts and the like. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium complex compound such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salts, sodium salts, potassium salts, etc.).

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

These metal complexes can be used in the same manner as the rhodium complex.

As the ligand of the metal complex, nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate coordination are used. Child, thiocyanate ligand, selenocyanate ligand, tellurocyanate ligand, acid ligand and aco ligand. When an aco ligand is present, it preferably occupies one or two of the ligands.

The addition amount of these metal complexes is adjusted depending on the use of the light-sensitive material, but is preferably in the range of 1.0 × 10 ⁻⁸ mol to 1.0 × 10 ⁻⁴ mol per mol of silver halide. Used. For example, in a light-sensitive material suitable for high-intensity exposure such as scanner exposure and a light-sensitive material for line drawing, 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ per mol of silver in a silver halide emulsion.
It is preferably used in a molar range, more preferably 8 × 10 ⁻⁷ to 1 × 10 ⁻⁶ mol.

The silver halide emulsion used in the light-returning light-sensitive material for a bright room contains 1.0 × 10 1 mol per mol of silver halide.
It is preferably used in the range of ⁻⁶ mol to 1.0 × 10 ⁻³ mol. More preferably, 1.0 * 10 <^-5> mol-1.
0 × 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

The halogen composition of the silver halide emulsion used in the present invention is silver chloride, silver chlorobromide or silver chloroiodobromide having a silver chloride content of 90 mol% or more. The content of silver iodide is preferably less than 5 mol%, particularly preferably less than 2 mol%.

The photographic emulsion used in the present invention is P. Glafki.
des by Chimie et Physique Photographique (Paul Mo
Published by ntel, 1967), Photographi by GFDufin
c Emulsion Chemistry (The Focal Press, 1966
Year), Making and Coating Photo by VLZelikman et al
graphic Emulsion (The Focal Press, 1964)
It can be prepared using the method described in, for example.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (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, grains can be formed by using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. A preferred compound is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione.

The controlled double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and are 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,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above paragraph to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 20% or less, particularly preferably 15%.
It is as follows. In the monodisperse silver halide emulsion of the present invention, the average grain size of grains in the emulsion is 0.25 μm or less,
Particularly preferably, it is 0.08 μm to 0.20 μm.

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

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 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 capable of producing silver telluride, which is presumed to become a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and the compounds described in Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

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

Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium. Specific examples of the gold sensitizer include chloroauric acid, potassium chlorate, potassium aurithiocyanate, gold sulfide, etc., and 10 ^-7 to 10 -10 per mol of silver halide
^{About -2} mol can be used.

As the reduction sensitizer used in the present invention, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt and the like may coexist in the process of formation of silver halide grains or physical ripening. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in European Patent Application (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, those having different crystal habits, and those having different conditions of chemical sensitization) may be used in combination.

The present invention may contain a spectral sensitizing dye depending on the use of the light-sensitive material. The spectral sensitizing dye used at that time is not particularly limited.

The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but is used in the range of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. To be

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 used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in Section 1X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
No. 62247, JP-A-2-48653, U.S. Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
No. 18, JP-A-62-284343, JP-A-2-10
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
No. 32, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242 and JP-A-3-67242, and general formula (IIIa) and general formula (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and a 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 Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978)
(Published monthly), page 23, IV, J.

For an argon laser light source, specifically, S1-1 to S1 described in Japanese Patent Application No. 7-179663.
The dye of -13 is particularly preferably used.

In addition to the above, the helium-neon light source is represented by the general formula (I) described in Japanese Patent Application No. 4-228745, page 8, line 1 to page 13, line 4 to line 4. Particularly preferred are sensitizing dyes. In addition, Japanese Patent Application No. 4-2287
The compounds described in General Formula (I) of No. 45 are also preferably used. Specifically, S2 described in Japanese Patent Application No. 7-179663
The dyes -1 to S2-10 are particularly preferably used.

For the LED light source and the infrared semiconductor laser, specifically, S described in Japanese Patent Application No. 7-179663 is used.
The dyes 3-1 to S3-8 are particularly preferably used.

For the infrared semiconductor laser light source, specifically, S4-1 to S described in Japanese Patent Application No. 7-179663.
The dyes 4-9 are particularly preferably used.

For a white light source for photographing with a camera, the sensitizing dye of the general formula (IV) described in Japanese Patent Application No. 5-201254 (page 20, line 14 to page 22, line 23) is preferably used. . Specifically, the dyes S5-1 to S5-20 described in Japanese Patent Application No. 7-179663 are particularly preferably used.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used.

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

A compound represented by the general formula ((a)) described in JP-A-1-118832, which has substantially no absorption maximum in the visible region. Specifically, the compound (a) described in the publication
-1 to (a) -26 compounds.

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

The polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20.

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
Conductive substances from the third line to the seventh line on the upper right of page 3 of the publication. Specifically, the metal oxides described on page 2, lower right line 2 to page 10, lower right line, and the conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

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

Solid disperse dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773.

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 fluorine-containing surfactants. Specifically, compounds (f) -1 to (f) -15 described in the same publication. Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1), the general formula (R-2), and
A redox compound represented by the general formula (R-3). Specifically, compounds of compounds R-1 to R-68 described in the publication.

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

The developer of the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). Any of known methods can be used for the development processing of the present invention. There is no particular limitation on the developing agent used in the developing solution of the present invention, but it is preferable that the developing agent contains dihydroxybenzenes or an ascorbic acid derivative. Further, in view of developing ability, dihydroxybenzenes and 1-phenyl-3-pyrazolidones are included. , A combination of dihydroxybenzenes and p-aminophenols, an ascorbic acid derivative and 1-
A combination of phenyl-3-pyrazolidones or a combination of ascorbic acid derivative and p-aminophenol is preferable, and a most preferable combination is a combination of ascorbic acid derivative and p-aminophenol.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
There are hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. The ascorbic acid derivative developing agent preferably used in the present invention is a compound represented by formula (R).

[0153]

Embedded image

In the general formula (R), R ₁ and R ₂ are respectively a hydroxy group and an amino group (having 1 carbon as a substituent).
To 10 alkyl groups such as methyl group, ethyl group, n-
Includes those having a butyl group, a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-
A toluenesulfonylamino group, an alkoxycarbonylamino group (a methoxycarbonylamino group, etc.), a mercapto group, and an alkylthio group (a methylthio group, an ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group,
Or an atom group necessary for bonding P and Q to form a 5- to 7-membered ring together with two vinyl carbon atoms substituted with R ₁ and R ₂ and a carbon atom substituted with Y. Represents
Specific examples of the ring structure, -O -, - C (R 4) (R 5) -,
_{-C (R 6) =, -} C (= O) -, - N (R 7) -, - N
= And are combined. Where R ₄ , R ₅ , R
₆ , R ₇ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a substituent may be a hydroxy group, a carboxy group, a sulfo group), a hydroxy group,
Represents a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include dihydrofuranone ring, dihydropyrone ring, pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolinone ring, pyridone ring, azacyclohexenone ring, uracil ring and the like. And preferred examples of the 5- to 7-membered ring are:
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azasiloxhexenone ring,
A uracil ring can be mentioned.

Y is a group composed of ═O or ═N—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), a carboxy group. Represents an alkyl group (for example, carboxymethyl, carboxyethyl). Specific examples of the compound represented by formula (R) are shown below, but the invention is not limited thereto.

[0158]

Embedded image

[0159]

Embedded image

[0160]

Embedded image

[0161]

Embedded image

Of these, ascorbic acid and erythorbic acid (diastereomers of ascorbic acid) are preferred. A general range of the amount of the compound of the general formula (R) used is 5 × 10 ⁻³ per liter of the developing solution.
Mol to 1 mol, particularly preferably 10 ^-2 mol to 0.5 mol.

Further, 1-phenyl-3-used in the present invention
As developing agents for pyrazolidone or its derivatives, there are 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. . Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. Among them, N-methyl-p-aminophenol is preferable. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably, it is in the range of 0.2 to 0.6 mol / liter. Dihydroxybenzenes and 1
When using a combination of -phenyl-3-pyrazolidones or p-aminophenols, the former is 0.05 to
0.6 mol / liter, more preferably 0.2-0.
5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter or less. The ascorbic acid derivative developing agent is usually preferably used in an amount of 0.05 to 1.0 mol / liter. Particularly preferably, it is in the range of 0.1 to 0.5 mol / liter. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
~ 1.0 mol / liter, more preferably 0.1
It is preferred to use 0.5 mol / liter, the latter 0.2 mol / liter or less, more preferably 0.1 mol / liter or less.

Examples of the preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
When a dihydroxybenzene type developing agent is used, the amount of sulfite is 0.20 mol / liter or more, particularly 0.3 mol / liter.
It is used in an amount of 1 liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is preferably 1.2 mol / liter. Particularly preferably 0.35
~ 0.7 mol / l. On the other hand, when an ascorbic acid derivative developing agent is used, the amount of sulfite may be small and may be 0.5 mol / liter or less.

When a dihydroxybenzene type developing agent is used, a small amount of an ascorbic acid derivative may be used in combination with sulfite as a preservative. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The addition amount is 0.03 in molar ratio with respect to the dihydroxybenzene type developing agent.
To 0.12 is preferable, and 0.05 is particularly preferable.
The range is from 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

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

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

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

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include those disclosed in JP-A Nos. 52-102726, 53-42730 and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, as a development unevenness preventive agent, JP-A-62-
Compounds described in No. 212,651 as dissolution aids
The compound described in 1-267759 can be used. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent,
It may contain a hardener or the like.

The development temperature and time are interrelated and are determined in relation to the total processing time. Generally, the development temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C.
The development time is 5 seconds to 2 minutes, preferably 7 seconds / 1 minute 30 seconds.

In the present invention, both the development starter solution and the development replenisher solution have the property that "the pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.25 or less". It is necessary. The method of confirming that the development starter solution or development replenisher used has this property is as follows.
Is adjusted to 10.0, then 0.1 mol of sodium hydroxide is added to 1 liter of this solution, and the pH value of the solution at this time is measured. It is determined that it has the property. In the present invention, it is particularly preferable to use a development starter solution and a development replenisher solution which have a pH value increase of 0.2 or less when the above test is carried out.

As a method for imparting the above-mentioned properties to the development initiating solution and the development replenishing solution, it is preferable to use a buffer.
Examples of the buffer include carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93333 (eg, saccharose), oximes (eg, acetoxime), and phenols (eg, 5 -Sulfosalicylic acid), tertiary phosphates (e.g., sodium salts, potassium salts) and the like, preferably carbonates and boric acid. The amount of buffer, especially carbonate used, is preferably
0.5 mol / liter or more, particularly 0.5 to 1.5 mol /
Liters.

As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

In the present invention, the pH of the development initiating solution is 8.5 to 12.0, particularly preferably 9.0 to 1.
It is in the range of 1.0. The pH of the developer replenisher and the pH of the developer in the developing tank during continuous processing are also in this range. p
As the alkali agent used for setting H, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

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

For the purpose of transporting the processing solution, packaging material cost, space saving, etc., it is preferable to concentrate the processing solution and dilute it before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. It is particularly preferably 0.2 to 1.5 mol / liter. The fixing solution may optionally contain a hardening agent (eg, a water-soluble aluminum compound), a preservative (eg, a sulfite,
Bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid), a chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
No. 58-122536, alcohols having a triple bond in the molecule, U.S. Pat.
A thioether compound described in JP-A-126449;
And the like, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid; and inorganic acids such as boric acid, phosphate, and sulfite. Buffers can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing the pH of the fixing agent from increasing due to carry-in of the developing solution, and 0.01 to
1.0 mol / liter, more preferably 0.02 to 0.1.
Use about 6 mol / l. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

As the hardener in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C. to about 50 ° C., preferably 25 ° C.
At ~ 45 ° C, the fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is 500 ml / m ² or less, particularly preferably 200 ml / m ² or less, based on the processing amount of the photosensitive material.

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. For washing or stabilizing treatment, the amount of washing water is usually 2 per 1 m2 of silver halide light-sensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-28725. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 235
As described in JP-A-133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles which are easily generated at the time of washing with a small amount of water and / or to prevent a treatment agent component adhering to a squeeze roller from being transferred to a treated film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. If necessary, metal compounds such as ammonium compounds, Bi, and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines, and surfactants may be used in this stabilizing bath. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferred.

The processing liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be in the form of a powder and solidified. Known methods can be used, but it is preferable to use the methods described in JP-A-61-259921, JP-A-4-85533, and JP-A-4-16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Four steps of a stabilization step may be used instead of the washing step. Hereinafter, the present invention will be described in more detail with reference to Examples.

[0183]

【Example】

Example 1 <Emulsion preparation> Emulsion A: 3 x 10 ^-5 mol of sodium benzenethiosulfonate per mol of silver and sodium chloride kept at 38 ° C, 3 x 10 ^-3 mol of 4-hydroxy-6-methyl-
PH containing 1,3,3a, 7-tetrazaindene = 2.
An aqueous solution of sodium chloride containing 4 × 10 ^-5 mol of K ₂ Ru (NO) Cl ₅ per mol of silver in a 1.5% gelatin aqueous solution of 0 was finally prepared by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds. Half of the silver amount of the particles was added at the same time to prepare core particles of 0.12 μm. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 4 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes to give a silver chloride cube having an average particle size of 0.13 μm. Particles were prepared. (Coefficient of variation: 12%) After that, washing with water by a flocculation method well known in the art to remove soluble salts, gelatin was added,
Compound-A and phenoxyethanol as preservatives in silver 1
After adding 60 mg per mole, pH 5.5, pAg =
After adjusting to 7.5 and adding 4 × 10 ⁻⁵ mol of chloroauric acid to 1 mol of silver, 1 × 10 ⁻⁵ mol of sodium thiosulfate and 1 × 10 ⁻⁵ mol of selenium compound SE were added. In addition, after heating at 60 ° C. for 60 minutes for chemical sensitization, 4-hydroxy-6-methyl-1,3,3 as a stabilizer was added.
1 × 10 ⁻³ mol of a, 7-tetrazaindene was added per mol of silver (as final particles, pH = 5.5, pAg =
7.5, Ru = 4 × 10 ⁻⁵ mol / Ag mol).

Emulsion B: K doped in grain formation
₂ Prepared exactly as in Emulsion A except that the amount of Ru (NO) Cl ₅ was 7 × 10 ⁻⁵ mol / Ag mol.

<Preparation of Emulsion Layer Coating Solution A and Coating> The following compounds were added to Emulsion A, and gelatin coating amount was 0.45 g / m ² and silver coating amount was 1 on the following support including the undercoat layer. .38
The silver halide emulsion layer A was coated so as to have g / m ² . Sodium 3- (5-mercaptotetrazole) benzenesulfonate 5.5 mg / m ² N-oleyl-N-methyltaurine sodium 10 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² Hydrazine compound H-10e 7.5 mg / m ² Compound-B 6.6 mg / m ² Compound-C 7.5 mg / m ² Nucleation accelerator B-14 10 mg / m ² Polymer latex (Compound-D) Sodium ascorbate 0.5 mg / m ² Compound-E (hard Membrane agent) The amount at which the swelling rate of distilled water at 25 ° C for 1 minute on the emulsion side after coating is 80%

<Preparation of Emulsion Layer Coating Solution B and its Coating> The following compounds were added to Emulsion B, and the gelatin coating amount was 0.45 g / m ² and the coating silver amount was 1.38 g / m in the upper layer of Emulsion layer A. The silver halide emulsion layer B was coated so as to be m ² . Sodium 3- (5-mercaptotetrazole) benzenesulfonate 5.5 mg / m ² N-oleyl-N-methyltaurine sodium 10 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² Hydrazine compound Hz-1 7.5 mg / m ² Compound-B 6.6 mg / m ² compound-C 7.5 mg / m ² compound-D 10 mg / m ² polymer latex (compound-D) sodium ascorbate 0.5 mg / m ² compound-E (hardener) coating Amount of swelling rate of distilled water of 80% after 1 minute at 25 ° C on the emulsion side

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer. <Preparation of Emulsion Protection Lower Layer Coating Solution and Its Coating> The following compound was added to an aqueous gelatin solution, and the gelatin coating amount was 0.8 g / g.
It was applied as a m ^2. Gelatin (Ca ⁺⁺ content 2700ppm) 0.8g / m ² p- Sodium dodecylbenzenesulfonate 10 mg / m ² of polystyrene sulphonic acid 6 mg / m ² Compound -A 1 mg / m ² Compound -F 14mg / m _² C ² H ₅ SO ₂ SNa 3 mg / m ² compound-H 20 mg / m ²

<Preparation of Emulsion Protecting Upper Layer Coating Liquid and Its Coating>
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.45g / m ² amorphous silica matting agent 40mg / m ² (average particle size 3.5μ, pore diameter 25Å, surface area 700m ² / g) amorphous silica matting agent 10mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycinpottadium 5 mg / m ² p-sodium dodecylbenzenesulfonate 30 mg / m ² compound- A 1 mg / m ² liquid paraffin 40 mg / m ² solid disperse dye-G ₁ 5 mg / m ² solid disperse dye-G ₂ 70 mg / m ² sodium polystyrene sulfonate 4 mg / m ²

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated on both sides with the first and second undercoat layers having the following compositions. <Undercoat first layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-M 0.20 g colloidal Silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. 2 The dry film thickness is 0.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-N 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-A 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm, to prepare a support including an undercoat layer.

Then, a conductive layer and a back layer shown below were simultaneously coated on the side of the support opposite to the side coated with the emulsion layer. <Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 186 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ² p-sodium dodecylbenzenesulfonate 13 mg / m ² dihexyl-α-sulfo Succinate sodium 12 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Compound-A 1 mg / m ²

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94mg / m ² Polymethyl methacrylate fine particles (average particle size 3.4μ) 15mg / m ² Compound -H 140 mg / m ² Compound -I 140 mg / m ² Compound -J 30 mg / m ² compound-K 40 mg / m ² p-sodium dodecylbenzenesulfonate 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ² compound-L 5 mg / m ² N-perfluorooctane sulfonyl-N-propyl Glycine Potassium 5 mg / m ² Sodium sulfate 150 mg / m ² Sodium acetate 40 mg / m ² Ethyl acrylate / acrylic acid (99/1 wt%) copolymer (polymer latex) 195 mg / m ² Compound-E (hardener) Amount at which the swelling ratio of distilled water at 100 ° C. for 1 minute at 25 ° C. on the back surface side after coating was 100% The coating sample A was prepared as described above.

[0193]

Embedded image

[0194]

Embedded image

[0195]

Embedded image

[0196]

Embedded image

[0197]

Embedded image

Further, coating sample B was prepared in the same manner as coating sample A except that H-10e was not contained, and coating sample C was prepared in the same manner as coating sample A except that B-14 was not prepared.
Application sample D was prepared in the same manner as application sample A except that 10e and B-14 were not included.

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The prepared sample was FDA-made by Dainippon Screen Co., Ltd.
An 800FX (using Fresnel lens) printer is used to expose through a step wedge, and Fuji Photo Film Co., Ltd.
Using an automatic developing machine FG-680AG, the following developing solution was processed at 38 ° C. for 20 seconds, and then fixing, washing and drying were performed. The fixer used had the following composition.

Developers 101-115 Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4-Hydroxymethyl-4 -Methyl-1 phenyl-3-pyrazolidone 0.45 g Compound of the present invention Amount of compound shown in Table 9 shown in Table 9 Sodium erythorbate 3.0 g Potassium hydroxide is added, and water is added to make 1 liter. PH is 10.5. To match.

[0201]

[Table 9]

The fixing solution used had the following formulation. (Fixing solution formulation) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (Adjust with sulfuric acid or sodium hydroxide) 4.85 Add water to 3 liters

(2) Evaluation of Sensitivity Sensitivity was expressed by the relative value of the logarithmic value of the exposure amount giving a density of 1.5. The coated sample 1 was developed at a temperature of 38 ° C. using the developer 101
The sensitivity at the time of second development processing was set to 100.

(3) Contrast of image As an index (gamma) indicating the contrast of an image, fog + density of 3.
Points of 0 were 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) / [l
og (exposure to give a density of 3.0)-(exposure to give a density of 0.1)], indicating that the larger the gamma value, the harder the photographic characteristics.

(4) Evaluation of Extracted Character Image Quality With regard to the extracted character image quality 5, it is suitable to use a document as shown in FIG. 1 so that 50% halftone dot area is 50% halftone dot area on the return photosensitive material. It is an image quality in which a character with a width of 30 μm is reproduced when exposed, and it is a very good extracted character image quality. On the other hand, the blank character image quality 1 is an unexplained blank character quality that can reproduce only a character having a width of 150 μm or more when the same appropriate exposure is given. Rank is set. Three or more is a practical level.

(5) Evaluation of running process Fuji Photo Film Co., Ltd. automatic processor FG-680AG
The developer and fixer are filled in and the coating sample 1 is applied 100 times a day.
After treating with m ² for 10 days at 38 ° C. for 20 seconds, the sensitivity, contrast, and character quality of blank characters were evaluated.

(6) Evaluation of Silver Contamination After running, unexposed Fuji Photo Film Co., Ltd. contact paper sensitive material KU-150WP (cut into 4 pieces)
Was treated and the degree of adhesion of dirt was evaluated on a 5-point scale. 5
Is the best level, 1 is the worst level, and 4 and above are practically acceptable levels.

(7) Evaluation of Fixability After the running treatment, the fixing treatment temperature was changed to 15 ° C. and the unexposed coating samples A to D were treated, and 10 sheets were covered.
The transparency was visually evaluated in five levels. 5 is the best level, 1 is the worst level, and 4 and above are practically permissible levels.

[0209]

[Table 10]

<Results> From Table 10, an image processing method satisfying all of the sensitivity, the image quality of characters without blank, the stability in running, the silver stain and the fixing property when the photosensitive material not using the compound of the present invention and the developing solution is used. It turns out that can't be obtained.

Example 2 The same evaluation as in Example 1 was conducted except that the developing solutions 201 to 215 were changed, and the results shown in Table 12 were obtained.

Developers 201 to 215 Water 700 ml Sodium hydroxide 2.5 g Diethylenetriaminepentaacetic acid 4.0 g Potassium carbonate 27.5 g Sodium carbonate monohydrate 25.5 g Potassium bromide 3.0 g Sodium sulfite 5.0 g Compounds of the invention Table 11 Amount of compound shown in Table 11 N-methyl-p-aminophenol 7.5 g Sodium erythorbate 30.0 g Adjust pH to 9.7 and add water to make 1 liter.

[0213]

[Table 11]

[0214]

[Table 12]

From Table 12, even if the composition of the developer is changed,
It can be seen that the compounds of the present invention are effective.

Example 3 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion 3-A was prepared by the following method. (Emulsion 3-A) Aqueous silver nitrate solution, potassium bromide, sodium chloride, K ₃ IrCl ₆ corresponding to 3.5 × 10 ^-7 mol and 1 K ₂ corresponding to 2.0 × 10 ^-7 mol per mol of silver. R
Halogen salt aqueous solution containing h (H ₂ O) Cl ₅ , sodium chloride, and gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione were added by a double jet method with stirring to obtain an average particle size of 0.20 μm. ,
Silver chlorobromide grains having a silver chloride content of 90 mol% were prepared.

Thereafter, the product was washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added per 1 mol of silver, 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver, and the pH was adjusted to 6.0. The pAg was adjusted to 7.5, 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. for optimum sensitivity.
Then, as a stabilizer, 4-hydroxy-6-methyl-
150 mg of 1,3,3a, 7-tetrazaindene was added, and further 100 mg of proxel as a preservative was added. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.20 μm and a silver chloride content of 90 mol%.
(Coefficient of variation 10%)

(Emulsion 3-B) At the time of grain formation, silver chlorobromide cubic grains containing 85 mol% of silver chloride were prepared in the same manner as in Emulsion 3-A except that the ratio of sodium chloride and sodium bromide was changed. Further, it was chemically sensitized in the same manner as Emulsion A.
The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 85 mol%. (Coefficient of variation 10%)

Preparation of Coating Sample E On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, from the support side,
Application samples E were prepared by sequentially applying the layers so as to have a UL layer, an EM layer, a PC layer, and an OC layer. The preparation method and application amount of each layer are shown below.

(UL layer) A dispersion of 30% by weight of polyethyl acrylate in gelatin was added to an aqueous gelatin solution and coated so as to have a gelatin content of 0.5 g / m ² .

[0221] in (EM layer) The Emulsion 3-A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2) And 3 × 10 ⁻⁴ mol of the mercapto compound represented by (a) below, 4 × 10 ⁻⁴ mol of the mercapto compound represented by (b), and 4 × 10 ⁻⁴ mol of (c) per mol of silver. The indicated triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, and nucleation accelerator A-12 were added in 4.4 × 10 ⁻⁴ mol. Furthermore, 100 mg of hydroquinone and N-oleyl-N-methyltaurine sodium salt were added so as to be coated at 30 mg / m ² . Next, add nucleating agent H-2b at 5 × 10 ^-4
mol / Agmol, (d) water-soluble latex 2
00 mg / m ² , ² parts of polyethyl acrylate dispersion
00 mg / m ² , methyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2
-Acetoacetoxyethyl methacrylate latex copolymer (weight ratio 88: 5: 7) 200 mg / m ² ,
200 mg of colloidal silica with an average particle size of 0.02 μm
/ M ² , and 200 mg / m ² of 1,3-divinylsulfonyl-2-propanol was added as a hardening agent. The pH of the solution was adjusted to 5.65 using acetic acid. They were coated so that the coated silver amount was 3.5 g / m ² .

(PC layer) A dispersion of 50 wt% ethyl acrylate in gelatin aqueous solution, and
The following surfactant (w) was added at 5 mg / m ² , and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² , and gelatin was applied at 0.5 g / m ² . .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 4 having an average particle size of about 3.5 μm 4
0 mg / m ² , colloidal silica 0.1 g / m ² , polyacrylamide 100 mg / m ² and silicone oil 2
0 mg / m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (e) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate were coated.

[0224]

Embedded image

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0226]

Embedded image

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0228]

Embedded image

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

Preparation of Coating Sample F Coating Sample F was prepared in the same manner as Coating Sample E except that Emulsion 3-B was used.

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 488 nm and a step wedge to emit light at a light emission time of 10 ⁻⁵ se.
After being exposed to the xenon flash light of c and developed at 35 ° C. for 30 seconds using the developing solutions 101 to 115 having the composition described in Example 1, fixing (described in Example 1), washing with water, and drying treatment. went.

(2) Evaluation of sensitivity Evaluation was carried out in the same manner as in Example 1.

(3) Image Contrast Evaluation was carried out in the same manner as in Example 1.

(4) Evaluation of smoothness of halftone dots Using an Argon light source color scanner M-656 manufactured by Crossfield Co., Ltd., 50% of flat mesh was output to the coated light sensitive material at 100 lines, and Perform development processing under processing conditions,
Visually evaluate the smoothness of halftone dots with a 200x magnifier,
Evaluation was made by a 5-point method of (good) 5 to 1 (bad). 4 in practice
Need more than points.

(5) Evaluation of running performance The same operation as in Example 1 was carried out.

(6) Evaluation of silver stain The same procedure as in Example 1 was carried out.

(7) Evaluation of Fixability The same procedure as in Example 1 was carried out.

[0238]

[Table 13]

<Results> From Table 13, the sensitivity, the image quality (smoothness), the stability during running, and the stability when running were evaluated only when a coating sample having a silver chloride content of 80% or more was treated with the developer containing the compound of the present invention. It can be seen that an image processing method that satisfies all of silver stain and fixability cannot be obtained.

Example 4 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion 4-A was prepared by the following method. [Emulsion 4-A] Except for chemically sensitizing at 60 ° C. by adding 1 mg of a selenium sensitizer having the following structural formula, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid per mol of silver. Was prepared in the same manner as Emulsion 3-A.

[0241]

Embedded image

Preparation of coating sample In place of the sensitizing dye of the EM layer of Example 3, the following compound (S-3) was added in an amount of 2.1 × 10 ⁻⁴ mol per mol of silver to prepare an emulsion for the EM layer. A sample was prepared in the same manner as in Example 3 except that Emulsion 4-A was used.

[0243]

Embedded image

<Evaluation of Photographic Performance> (1) Exposure and Development Processing The above sample was passed through an interference filter having a peak at 633 nm and passed through a step wedge to emit light for 10 ⁻⁶ se.
The substrate was exposed to xenon flash light of c. After developing with the developing solutions 101 to 115 described in Example 1 at 35 [deg.] C. for 30 seconds, fixing (same as in Example 1), washing with water, and drying were performed.

The sensitivity, image contrast, and halftone dot smoothness evaluation, running performance, silver stain, and fixability were the same as in Example 3. However, for exposure, a He-Ne light source color scanner Dreb 800 manufactured by Cytex Co., Ltd. was used.

<Results> By using the compound of the present invention, it was possible to obtain an image forming method capable of stably processing a light-sensitive material for a helium neon laser scanner having a high gamma and a good halftone dot smoothness.

Example 5 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 4 except that the sensitizing dye in the EM layer of Example 4 was changed to the following compound (S-4). Created.

[0248]

Embedded image

<Evaluation of Photographic Performance> The above sample was tested for 780n.
Through an interference filter having a peak at m, it was exposed with a xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge. After developing with the developer A described in Example 1 for 30 seconds at 35 ° C., fixing (the same as in Example 1), washing with water, and drying were performed. The image contrast evaluation and the halftone dot smoothness evaluation were performed in the same manner as in Example 1. However, an LD light source color scanner Luxscan 4500 manufactured by Fuji Photo Film Co., Ltd. was used for the exposure. <Results> By using the compound of the present invention, it was possible to obtain an image forming method for stably processing a photosensitive material for a semiconductor laser scanner having a high gamma and a good halftone dot smoothness.

Example 6 Instead of the developing solutions 101 to 115 used in Examples 3 to 5,
Using the developing solutions 201 to 215, the photosensitive materials prepared in Examples 3 to 5 were developed under the conditions of the respective Examples.

<Results> The effect of the compound of the present invention did not change even if the composition of the developing solution was changed.

Example 7 Developers having the compositions of Developers 101 to 115 were prepared from solid storage forms. Developers 301 to 315 In the method for producing a solid processing agent, the components of the developer were solidly laminated and packed in a bag made of an aluminum foil coated with a plastic material. The order of lamination is from the top, first layer Hydroquinone Second layer Other components Third layer Sodium bisulfite Fourth layer Potassium carbonate Fifth layer Potassium hydroxide pellets, evacuate by conventional method, evacuate the system Sealed.

<Results> In the development processing of Examples 1, 3 to 6,
Even when the developing solutions 301 to 315 were used, the same results as those in the liquid storage form (developing solutions 101 to 115) were obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication G03C 5/305 G03C 5/305

Claims (1)

[Claims] 1. A support having at least one silver halide emulsion layer, wherein the silver halide emulsion contains at least one transition metal of Group V to Group VIII at 1 × 10 ^{−8 with} respect to 1 mol of silver.
The content of silver chloride contained from 1 to 10 ^-4 mol 90 mol%
Silver halide grains comprising silver halide grains having an average grain size of 0.25 μm or less and at least one of the emulsion layer and the other hydrophilic colloid layer containing a hydrazine derivative and a nucleation accelerator. An image forming method, which comprises treating a photographic light-sensitive material with a developer containing a compound represented by the general formula (1). General formula (1) In the formula, Z ¹ represents a non-metal atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle in cooperation with N and C, and Z ¹ represents R ¹ and (SX ² ) as a substituent. _{have n} .
Here, R ¹ represents a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. X ¹ and X ² are hydrogen atoms or cations, and n is 0, 1 or 2. Further, two kinds of radicals obtained by removing one arbitrary hydrogen atom from Z ¹ may combine to form a bis type structure.